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Hydroplumbation of Unsaturated Organic Compounds.

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condensation and subsequent dehydration to afford butenolides ( I ) .
R2
J
R
R
(1)
For example, treatment of 1-acetoxy-1-acetylcyclohexane (2),
R = H, in dimethyl sulfoxide with 1 mole of sodium hydride
for 5 h at room temperature yields 40 % P-[l'-hydroxycyclohexyllcrotonolactone (3), R = H [m.p. 49.5-51 OC, from
hexane, ~ 2 1 1= 13300, lactone band at 1752 cm-1 in a
KBr-pellet].
trimethyl-lead hydride onto ethylene have so far been described; the results are conflicting [2, 31.
Organolead hydrides of general formulae R3PbH and
RzPbHZ were known previously only with R = CH3 or
C2H5 [2-51. They decompose above -20°C, some even
already above -50 "C. In order to obtain compounds which
are easier to handle we used larger alkyl residues. We reduced
the corresponding chlorides in diethylene glycol dimethyl
ether at -60 "C with LiAIH4 and obtained good to excellent
yields of the hydrides.
Weaker complexing agents such as ether or tetrahydrofuran
allowed the reverse reaction to proceed, and decomposition
occurred during isolation. The products are decomposed by
light and extremely readily by air but can be kept for a few
days at least at 0 ° C in the dark.
[a] In cyclohexane. [bl In diethylene glycol dimethyl ether.
Similarly, l ~ a c ~ t ~ l - l - ~ ~ o ~ i o n ~ l o x ~ c ~ c ~ o h(2),
e x a n e = CH3,
gives rise to 45 % a-methyl-B-[l'-hydrox~c~clohexylIcrotonolactone (3), R = CH3 [m.p. 65-66 "C, from hexane, ~ 2 1 7=
13370, lactone band at 1750 Cm-' in cs2 Or at 1745 in a
KBr-pellet].
Tributyl-lead hydride adds even at low temperatures and
without a catalyst onto a-olefins, isocyanates, and alkynes to
(In)-(Ic), (2) and (3). The yields obtained with the pure hydride are 90-100 %. The adducts were freed from volatile impurities, distilled if possible, and characterized by their infraThe analogous reaction with 17a-acetoxy-As-pregnen-3P-01red spectra and by C, H, and p b analyses. Thus a new and
20-one (4) affords a 78 % yield of 3P,17a-dih~drox~-A~,~~(~~)very mild method for introducing plumbyl groups into
complicated molecules has been established, and numerous
norcholadienic-23 -+ 17-lactone (6), b . p . 257-259 'c, from
hexane/dichloromethane, E218 = 12000, lactone band at
organolead compounds containing functional groups 1743 cm-1 in chloroform or 1725 in a KBr-pellet].
hitherto a very small class of compounds [5] - have become
accessible.
x
......o
Further
products
The P-hydroxybutyrolactone intermediate (5) can be isolated
if the reaction of (4) is conducted with only catalytic amounts
of powdered sodium hydroxide in dimethyl sulfoxide at
20 "C and interrupted after 10 min. The 3@,17cr,20-trihydroxyAs-norcholenic-23 + 17-lactone (5) melts at 287-288 "C
[from ethyl acetate/methanol; lactone band at 1740 cm-1 in
a KBr-pellet].
Received: March 19th, 1965
[Z 9431769 IE]
German version: Angew. Chem. 77, 808 (1965)
Publication deferred until now at the author's request
Hydroplumbation of Unsaturated Organic
Compounds
ic] B.p. 116-119°C/0.01 mm.
[d] B.p 94-97°C/10-4
mm.
[el B.p. 128-130 W I O - 4 mm, with partial decomposition.
[fl The product reacts with both phenyl isocyanate and RIPbH. Depending on the conditions, a high yield of 1,3,5-triphenyl-isocyanuricacid or
of a crystalline compound is formed which decomposes at 170 to
172 "C and probably has the composition C~7H22N402.I n addition,
hexabutyldiplumbane can also be isolated.
[g]
This compound decomposes on being distilled.
Institut fur Organische Chemie der Universitat GieRen
(Germany)
n-Octene does not react under identical conditions. Pb-H
groups can be more reactive than Sn-H groups. Thus
acrylonitrile is not attacked by tributyltin hydride at O°C
without a catalyst within 20 hours, but tributyl-lead hydride
adds on completely within 8 hours under the same conditions.
Numerous unsaturated organic compounds, e.g. those with
C=C, C=C, C=N, or C=O groups, can be hydrostannated
111. In the organolead hydride series, only attempts to add
Alkyl halides can be reduced rapidly - often exothermally to alkanes.
R-I
R3PbH + R'-H
R3PbI
By Prof. Dr. W. P. Neumann and Dipl.-Chem. K. Kuhlein
784
+
+
Angew. Chem. internat. Edit. j Vol. 4(1965) J No. 9
Complexes of ( I ) with transition metal salts such as I\fiCh
or CoC12 are much less stable. No adduct formation was
observed in solvents. However, when the components are
fused together, green to blue substances are formed which discolor rapidly in moist air. The colored adducts have the com(M = Co or Ni) and have
position [(CsHs)~PNCbHs]2.MCI~
the magnetic moments expected for wzak complexes.
If the alkane is volatile, c.g.when R' = CzH5, this reaction
can be used for quantitative estimation of the organolead
hydride.
Benzyl chloride, o3-bromoacetophenone, ally1 bromide,
bromobenzene, and iodobenzene are dehalogenated in this
manner at 0 OC; triethyltin chloride gives rise to the hydride,
1,2-dibromoethane to ethylene, and carbon tetrachloride
selectively to chloroform or dichloromethane. Benzaldehyde
and nitrobenzene are also reduced at O°C.
Received: July 5 t h 1965
[Z 16/848 IEJ
German version: Angew. Chem. 77, 809 (1965)
[Z 14/839 1EJ
Received: J u n e 8th. 1965
German version: Angew. Chem. 77, 808 (1965)
Publication deferred until now at the authors' request
[I] H. Zimmer and C . Singh, J. org. Chemistry 29, 3412 (1964).
[2] D. Seyferth and S. 0. Grim, J. Amer. chem. SOC.83, 1610
(1961).
[3] L. Horiier and H. Oediger, Liebigs Ann. Chem. 627, 142
(1959).
[ I ] Reviewed by W. P. Neurnann, Angew. Chem. 76, 849 (1964);
H . G. Kuivila, Adv. organomet. Chem. I, 47 (1964).
[2] W . E. Eecker and S. E. Cook, J. Amer. chem. SOC.82, 6264
(1960).
131 R. Duffy, J. Feeney, and A. K . Holliday, J. chem. SOC.(Lon-
Phosphine SulfidelTin Halide Complexes
don) 1962, 1144.
[41 E. Amberger, Angew. Chem. 72, 494 (1960).
IS] Reviewed by L . C . Wzlleinsensr Organolead Chemistry.
Semper Avanti, Den Haag 1964.
By Dr. H. Teichmann
Institut fur Organische Chemie der Deutschen Akademie der
Wissenschaften, Berlin-Adlershof (Germany)
Although numerous adducts of tertiary phosphine oxides are
known, the only adduct of phosphine sulfides which has been
described is the compound [(C6H5)3PS]2PdC12[I]. We have
now found that trialkylphosphine sulfides react in inert
solvents such as dichloromethane or hexane with tin(1V)
chloride or bromide to give stable 2: 1 adducts. High to
quantitative yields of the compounds (1)-(10) were obtained
in this way. The 1 : 1 adducts ( 1 I ) - ( 1 4 ) were formed analogously from tetraalkylbiphosphine disulfides. The complexes
( I ) - ( 6 ) can be sublimed.
Complexes of Iminophosphoranes with Metal Salts
By Dr. W. Seidel
Institut fur Anorganische Chemie der Universitat Jena
(Germany)
Iminotriphenylphosphorane (triphenylphosphine imine) is a
member of the isoelectronic series (C&5)3PO - (C&j!3PNH
- (C6H5)3PCHzI in which the nucleophilicity increases
IR2RPSIz SnX4
R
X
1M
P. ["CI
166-6615
BL 176-77
C1
greatly from left to right. Reactions of the unsubstituted
imine and of its N-organo derivatives with hydrogen halides,
alkyl halides, and Lewis acids have been investigated [I].
However, nothing is known of its ability t o form adducts with
metal salts. The complexes of triphenylphosphine oxide have
been closely examined, and it is known that methylenetriphenylphosphorane condenses with mercuric bromide to give
([(C6H5hPCH&Hgf (HgBrdz [21.
We have found that phosphine imines R3PNR also form
adducts with metal salts. The stability of the adducts depends
largely on the nature of the N-substituent. N-Phenyliminotriphenylphosphorane, (C6135)3PNC6H5 ( I ) [31, reacts with mercuric or cadmium iodide in benzene/acetonitrile (1: 1 v/v)
to give the highly insoluble stable adducts
//
R
M.p. ["Cl
101-02
174-77
155-57
145-47
152-54
146-49
138-39
The electron-donor capacity of the sulfur bonded to phosphorus is less than that of oxygen, as shown by the reaction
of the adducts (I)-(14) with trimethyl phosphate at
room temperature, which releases the phosphine sulfides.
However, the adducts are stable towards ether.
The presence of a P = S +Sn coordination in the adducts follows from the bathochromic shifts of the P-S stretching
frequencies of u p to 45 cm-1.
Triphenylphosphine sulfide does not react with SnC14
etherate [l], but reacts with SnC14 in dichloromethane to give
an unstable adduct, which decomposes o n heating or o n
treatment with ether.
Received: June 281h, 1965
[Z18/840 IE]
___
German version: Angew. Chem. 77. SO9 (1965)
[ 11 E. Bannister and F. A. Cotron, J. chem. SOC. (London) 1960,
(CsH5)3PNCbH5.Hg12 (Z), yellow, m.p. 178 " c , yield 56 %,
and
(C~H~)~PNC~H~~CdI~(.?),colorless,
m.p. > 260 "C,yield78 %.
Compound (2) dissolves in methanol to give a colorless solution and is reprecipitated unchanged o n addition of water.
It is decomposed by 2 N nitric acid, HgIz being liberated. If
(2) is shaken with ether and a solution of potassium iodide in
water containing a little methanol, it is decomposed into
K2HgT4 and (I), the latter being extracted into the ether
phase. An analogous cleavage of (3) can be effected with a
solution of potassium cyanide.
Angew. Chem. internot. Edit. Vol. 4(1965)
1 No. 9
1959.
A One-Step Synthesis of y-Keto
Carboxylic Acids 111
By Dr. H. Reinheckel, Dr. K. Haage, and R. Gensike
Institut fiir Fettchemie der Deutschen Akademie der
Wissenschaften, Berlin-Adlershof (Germany)
Succinyl dichloride ( I ) is readily alkylated at -3OOC by
(CzIIs)3AlzC13 or C2H5AlC12 in a molar ratio of 1 :0.4 or
1 : 1.2 to yield y-oxocaproyl chloride, which occurs entirely in
785
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compounds, organiz, unsaturated, hydroplumbation
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