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Carbonylation of Lithium Dialkylamides to Give Carbamoyllithiums.

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( 3 ) , column chromatographic purification (Sephadex LH-20,
CH,CI,) of the resulting residue gave 79.2 mg (68%) of
phthalocyaninato[bis(tricarbonylrhenium)]tin ( 4 a ) as dark
green microcrystals.
Received: October 10. 197X [Z 179a IE]
German version: Angew. Chem. Y1.84 (1979)
M . Siiiitli' Porphyrins and Metalloporphyrins.
Elsevier. N w York 1974. p. 157: b) W R. Sc1ieidr. Acc Chem. Res.
[I] a ) ./. W Buchicr in K .
10, 339 (1977).
[ 2 ] a ) C. P. H r u i i g . Dissertation, Texas A & M University 1975; b) M .
7 s l i t s i i r . C . P. Hriiiig. D. Ostfu/rl. T S . Sriiric.laro, D. L. cO//i~Ji.
E. I;.
, Jr.. J . Am. Chem. Soc. 97, 3952 (1975).
JIIL'.
S B. S m l r u b i u i i . J. Organomet. Chem. 154, 273 (197X).
[4] CrystLik suitable for ;in X-ray structure analysis have still not been
obtained.
[ 5 ] I . .\odu. S. kulo, M . M i z u l u , N. Y r i ~ i i ~ l Vi ~. . Kusui. Angea. Chem.
91. X 5 11979): Angew. Chem. Int. Ed. Engl. I # . 83 (1979).
Fig. I . Structure of the carbido complex ( 4 1 [3]
A Metalloporphyrin Containing Carbyne-like Carbido
Carbon:
5,10,15,20-Tetraphenylporphyrinato[bis(pcarbidotricarbonylrhenium)]tin(~~)
[**I
By l p p r i Nodti, Sliinzi Ktrto, Musateru Mizutti, Norituke
YrisuoAti, and Nohurumi Kusui[*]
The green 5,10,15,20-tetraphenylporphinato[bis(tricarbonylrhenium)]tin(iv) f3)1'1 is formed on reaction of the dichloro
compound ( I ) with decacarbonyldirhenium (2) at 180°C.
Interestingly, however, we have found that the same reaction
at 160- 165°C affords a dark red complex ( 4 ) , showing similar
1R spectroscopic data to those of ( 3 ) . An X-ray structure
analysis["' of ( 4 1 , revealed it as being, to our knowledge,
the first metalloporphyrin containing carbido-carbon ligands.
distance (0.603 A)r51in common acetylene compounds]. The
Sn-C1 length (2.14 A) is in good agreement with the length
of the Sn-C single bonds in MezCISnSC(S)NMe,''l [2.17(5)
and 2.20(5) A]. Further, it is interesting that the Sn-CIERe
angle is 138.5(8)".Thus, the S n - e R e linkage is nonlinear.
We connot as yet offer a reasonable explanation for this
finding. The angles N1-Sn-C1
and N2-Sn-C1
are 89.4(5)
and 90.6(5)", respectively. The porphyrin ring is planar within
0.7A; Sn, N I , N2, N3 and N4 lie in a plane. Two Sii-N
lengths [2.07(2)w] are equal, the N-Sn-N
angles are 89.3(6)
and 90.1(6)", and the other bond lengths and angles also
have values in the usual range. At the present time, it is
unclear whether ( 4 ) is converted into ( 3 ) or not on heating
to 1 8 0 ~ ' 7 1 .
Received: October 10, 1978 [Z 129b IE]
German version: Angew. Chein. Y1. 85 (1979)
Sn(TPP)[Fie(C0)312 13)
l?
Sn(TPP)C12 + Rez(C0)lo
(1)
(2)
i
(180T) !
S n ( T P P ) [ l t e ( C 0 3 ) ( C ) ] z( 4 )
The compound ( 4 ) was prepared by a procedure similar
to that used previouslyl2I, from (1) and (2) by 240 hours'
heating at 160-165°C ~,,,,(CH2CI2):402 sh, 420 (Soret),
512, 552, 591 and 628nm; v ( G 0 ) (KBr): 2000, 1995, and
1920 cm '1. Small single crystals of ( 4 ) for X-ray crystallographic analysis were obtained on allowing a solution of the
complex in o-dichlorobenzene to stand for several weeks. As
shown in Figure 1 the centrosymmetric molecule contains
two R c ( C O ) ~groups, one located above and one below the
plane of the porphyrin ring which is centered by the tin
atom. Surprisingly, the tin and rhenium atoms are linked
by a carbido-carbon atom, which is bound carbyne-like to
the rhenium atom. The Re-Cl length (1.75 A) is close to
the Re=C distance (1.747A) which might be predicted from
the sum of the covalent radii [using half the Re=Re distance
(1.145A) in Re2C15.[MeS(CH2)2SMe)2[4J
and half the G C
~
~~
~.
[I] S. Kaio, I . N o h , M . Mizuru, Y. fi01i. Angew. Chem. Y l , 84 (19791:
Angew. Chem. Int Ed. Engl. 18, 82 (1979).
[ 2 ] M . T$ii!.\iii, C P Ifririiy, D. O.sr/t,/rl, 7: S. Sricii.srriia, 11. L. Cir//i~ii.t.
F . M e y r r , Jr.. J . Am. Chem. Soc. Y7, 3952 (1975).
[ 3 ] The structure was solved by the heavy-atom method and rcfined to
convergence ( R =0.0X4) using anisotropic temperature factors for all nonhydrogen atoms: S I ~ ( T P P ) [ R ~ ( C O ) ~ 2u-C,,HJCI,,
(C)]~
space group P1,:n
(NO. 14), a = 10.44(2), h = 13.48(1), c=20.19(2) A, p = I IO.X(I)", %=?,
pcxp=1.92, p,,,,=2.02
g cm-', p(Mo)=61.6 c m - I . Diffractometer with
graphite-monochromatized Mo-Ka radiation. w scan technique A.
A.>hii/u, The Universal Crystallographic Computing Program SystemOsaka. the Compiiter Center, Osaka University (1973).
.M ,/. BciiJiert. f.A . Colloii. R. .A. Wu/loii, J Am. Chcm. SOC.88. 3866
(I966).
L. I'airliiig'The Natureofthc Chemical bond. 3rd Edit. Corncll I'nivrrsity
Press, Ithaca 1960.
N . I u s i i i k i . N . Kosai. M . K ~ i u i i Bull.
~ . Chem. Soc. Jpn. 4 2 . 1601 (1970)
We have confirmed spectroscopically the conversion of ( 4 1 into ( 3 )
on heating at 180°C under excess of Re2(CO),o.
Carbonylation of Lithium Dialkylamides to Give
Carbamoyllithiums
~~
["I
Prof. Dr. S. Kato ['I, I. Noda, Prof. Dr. M. Mizuta
Departmcnt of Chemistr), Faculty of Engineering, Gifu University
Kagamihara. Gifu 504 (Japan)
Prof. Dr. N . Kasai ['I, Prof. Dr. N. Yasuoka
Department of Applied Chemistry, Faculty of Engineering, Osaka Universi t y
Yamadakami, Suita. Osaka 565 (Japan)
[ '3 Authors t o whom correspondence should be addressed.
[**I We wish to thank Professor Dr. A. Nrrkoin~ira and Dr.
K 4fiLi of'
Osaka University and Professor Dr. 7: Ashida and Prof. Dr. T Sakohr of
Nagoya University for useful comments.
By Valentin Ruutenstruucli and Miche/ Joyeux[*]
Authenticacyl anions would be useful as reagents in organic
synthesis' and as models for the study of acyl-transition
[*] Dr. V. Rautenstrauch
['I.
Dr. M Joyeux
Firmenich SA. Laboratoire de Recherche
h.p. 239. CH-I211 Geneve 8 (Switzerland)
['I Author to whom correspondence should be addressed: o n leave a t
the Department of Chemistry, Stanford University, Stanford, Calif. 94305
(USA).
83
metal compounds. Only certain carbamoyllithiums (CAL-s)
with presumably ionic, bent structures appear to be largely
persistent in solutionL2-'1 and thus represent an unexplained
"island of stability" in the area of acyl anions. Of the reported
modes of formation-namely (A) the addition of carbon monoxide to lithium dimethylamide[2d1or tert-butylamidera, "I,
(B) the transmetalation between butyllithium and bis(diethylcarbamoyI)mer~ury~~~,
and (C) the lithiation of dialkylformamides with lithium diis~propylamide[~~
or tert-butyllithiurn[']-the simplest, method (A), has been the least studied,
with contradictory results (cf.L21). We have investigated method
(A) in detail and report typical findings with two lithium
dialkylamides['I.
Passing C O into a ca. 0.6 M solution of lithium piperidide
in 1,2-dimethoxyethane (DME)/tetrahydrofuran(THF)/
hexane at cu. - 75°C under standard conditions [Procedure
(PR)] affords a solution of the corresponding CAL ( 3 ) , detectable by trapping reactions. Hydrolysis leads to the formamide
( 4 ) [yield based on ( 2 ) 20-30
hydrolysis with D 2 0
and workup with H 2 0 to the labeled formamide [D,]-(4)
along with small amounts of ( 4 ) [85 : 15 to 90: 10[7b1].Reaction
with cyclohexanone (0.6 equiv., PR) and hydrolysis gives the
hydroxycarboxamide ( 6 ) [m. p. 121-122"C] and in addition
the hydroxy(oxo)carboxamide (7) [m. p. 1 16-1 17 " C ; molar
ratio -4: I , yield ( 6 ) + ( 7 ) cu. 85 %[sal]. Similarly, reaction
with methyl iodide (PR) and hydrolysis affords the acetamide
( 8 ) and the 3-oxopropionamide ( 9 ) [z1 : I , yield ( 8 ) + ( 9 )
cu, 65
Reaction with (8) instead of methyl iodide under
otherwise the same conditions and subsequent hydrolysis likewise leads to ( 9 ) : addition of (3) to ( 8 ) thus competes
with the methylation of ( 3 ) ; protonation of the secondary
adduct leads to cleavage to give ( 9 ) and ( I ). (7) (and (I )) must
be formed analogously, by addition of (3) to the initially
formed alkoxide of (6), protonation of the secondary adduct,
and cleavage. (3) apparently does not react further with the
secondary adducts.
(2 )
(10)
113)
114)
Most lithium dialkylamides should react analogously with
CO to give CAL-s. Their synthetic utility is primarily limited
by 1 ) the reaction of the CAL-s with C O ; 2) the incomplete
conversions of the amides [in part due to I]; 3) the secondary
additions of unhindered CAL-s to primary adducts.
Procedure
20mmol of n-butyllithium (1.5-1.6 M) in hexane is added
t o 2 0 m m o l o f ( l ) o r (10) inDME(10ml)andTHF(10m1)[13]
at cu. -75°C under an inert gas and after 5 min C O is passed
(ca. 3I/h) at ca. -75°C for 4 h through the stirred solution. Hydrolysis: the solution (cu. -75°C) is poured into
ca. l00ml of H 2 0 (cu. 22°C). Hydrolysis with D2of9]:3ml
of D20 (ca. 22°C) is added at once to the stirred solution
(ca. -75°C) and the resulting mixture is diluted with H20.
Reaction with cyclohexanone or methyl iodide: 0.6 mol
of the substrates per mol of ( I ) or ( l a ) is added at cu.
-75"C,and the resultingmixtures are stirred for 3 h (CbH100)
or 1 h (CH,I) at -75°C and finally for 1 h at ca. 5 ° C ; hydrolysis as above. Isolation: The hydrolysates are diluted to en.
250ml with H 2 0 and continuously extracted with ether for
48 h. The extracts are concentrated and roughly fractionated.
Pure substances are obtained by gas chromatography andjor
recrystallization.
115)
Passing CO into a solution of lithium diisopropylamide
( 1 1 ) at cu. -75°C (PR) analogously affords a solution of
the corresponding, hindered CAL ( 1 2 ) . On reaction with
cyclohexanone, the secondary addition is suppressed, and
84
after hydrolysis ( 1 5 ) is obtained [m.p. 137-138"C,
yield ca. 50
Hydrolysis affords the formamide (13)
[yield based on (11) 20-40%'7i'1]; hydrolysis with D 2 0
and workup with H 2 0 gives the labeled formamide [Dl]-(13)
along with small amounts of (13) [84: 16 to 98:2[7b,91].
Both on prior (partial) trapping of (3) and ( 1 2 ) with cyclohexanone and subsequent hydrolysis [- ( 6 ) + ( 7 ) and
--t ( 1 S)] and on direct hydrolysis, the hydroxymalonamides
(S)[*'] [m.p. 81-82"CI and (14) [m.p. 102-103°C; yield
based on ( 1 1 ) or (1,U) (stoichiometry: 2 ( 1 0 ) + 3CO- (141,
10-20 0/0[7al] are isolated['"] along with the formamides ( 4 )
and (13). When CAL ( 1 2 ) is generated via method (C),
without introduction of CO, uiu the equilibrium
(If )+(13)+(10)+(12),
in concentrations comparable
with those obtained here on carbonylation (starting from cu.
0.5~
solutions of (11) and (13)) and in the same medium,
none of (14) is found on hydrolysis after leaving the reaction
.mixtures for 5 mjn ( 4 h ) to 4 h19] at cu. - 75 "C. This suggests
that the anionic precursors of (1 4 ) and ( 5 ) are formed by twofold addition of the CAL-s ( 1 2 ) and ( 3 ) to CO: the yield of
( 1 4 ) [a.
35% together with 20% of (13)] indeed increases
when more CO is introduced (PR. introduction of C O for 9
instead of 4h)["]. For this reason we have not attempted
to convert the lithium amides ( 2 ) and ( I 1 ) completely. Even
more (14) [yield ca. 40 %] is isolated when the carbonylation
is carried out at cu. 5°C (otherwise according to PR). ( I 2 )
presumably reacts with C O to give a short-lived adduct ( 1 6 ) ,
which rapidly adds ( 1 2 ) to give the dianion (17) of ( 1 4 )
(formation of the dianion of ( 5 ) analogous). Hydrolysis with
D 2 0 F 9and
] workup with H 2 0 indeed leads to labeled [D1](14)['21.
Received: May 22, 1978 [Z 72a IEJ
German version: Angew. Chem. Y l , 72 (1979)
. .~
[I]
D. Seehacli in R. Scheffold: Modern Synthetic Methods 1976. SauerIinder. Aarau 1976: in D. Seyfrrfli - New Applications of Organornetallic
Reagents in Organic Synthesis. Elsevier. Amsterdam 1976.
Arigeir. Cheni. I r i t . Ed. Eriql. 18 ( 1 Y7Y) N o . 1
[2] a ) P . I.iinqi, R . Morttuyiia. R . Mrr::occhi. Chim. Ind. (Milan) 4 7 . 480
(1965): b) P. Jurzi, E . W Sc/ir&fer, Angew. Chem. 83, 334 (1971): Angew.
Chem. Int Ed. Engl. 10. 339(1971).
[3] L'. Sihiililopf: I.. GerAnvr, Angew. Chem. 79. 819 (1967); Angew. Chem.
Int Ed. Engl. 6 . 805 (1967).Method (9) is an indirect variant of method
(A). aiiicc bis(diethylcarbamoy1)inercury is generated from Hg"-acetate,
dicthhlamtne and CO: L'. Sciiiillkopf, I;. Grrltarf, ibid. 78. 675 (19661,
and 5. 252 ( I 9661.
[4] a) B. Bdfthtdai. L'. Schiillkopf, Angew. Chem. 85. 861 (1973); Angew.
Chem. Int. Ed. tngl. 12, 836 (1973); b) R. R. Frasrr. P. R . Huberr.
Can. I . Chem. 52. 185 (19741; c ) U . S d i i j k i p J , H . B r c k h a u . ~Angew.
Chem 88, 296 (1976): Angew. Chem. Int. Ed. Engl 1 5 , 293 (1976);
.k. F. Efftiibrrger, R . GI
and 4. 951 (1965).
[5] 4. S t I~,rcher.K Smith. K . Swamirturhriii. J . Chem. Soc. Perkin Trans.
I l Y 7 7 . 1881.
[ 6 ] For the carbonylation of lithium moilo;llh\l;iniidc\ according to [2b]
see 1: Ruurmcrruuch. M . J o i e u u . A n g w . Cliciii 91. 7 3 (1979): Angew.
Chcin. Int. Ed. Engl. I#. 85 (1979).
[ 7 ] a1 Several runs. The variations in the yields are probably caused by
variations in the C O flow and by incomplete extraction (PR). b) Several
runs Control experiments with [Dt]-(4) and [Dt]-(J3) show that
no D l i exchange takes place during the isolation; ( 4 ) and ( 1 3 ) are
prohably formed i'iu method (C), on incomplete lithiation of the amines
f I I m d f 11)).
[8) a) Y ield not optimized. -b)The hydrolysate contains ( 13 ) and cyclohexanone. which probably reacts in part with unconsumed ( J l ) to give
the eiio1ate.- c) Yield not determined, of the same order as that of
(141.
[9] On hydrolysis of the solutions of ( I ? ) with a relatively small amount
of H 2 0 o r D 2 0 ( P R , hydrolysis with D z O ) the glyoxylamides ( J X )
and [D,]-fIX). respectively (cf. [4d]) [yield up to I S ' % based on
( I 1 I : only partially survives the extraction (PR)] o r their readily formed
hemihydrates ( 1 9 ) and [D,]-(IPI [ni.p. 103- -106°C (loss of water
t o give ( 18) and ID,]-( 18 J, wso-form)l are obtained in varying yields,
which long confused us: control experiments show that (18) (and/or
( I Y ) dnd!or the hydrate of ( 1 8 ) ) is formed after the addition of H,O
o r D 2 0 in the two-phase aystem consisting of the aqueous phase and
the cold (cu. -7F"C) DME;'THF/hexane solution, which contains ( I 1 J,
1191
1/81
[ 101
[I I]
[I21
[I31
amide (1 )['I rearranges rapidly to give the N-lithioformaniide
(31, as expected on the basis of the pK, values of (2).
Passing CO into ca. 0.6 M solutions of lithium dialkylamides
at cu. - 75 "C
in 1,2-dimethoxyethane/tetrahydrof~ran/hexane
under standard conditions affords the corresponding carbamoyllithi~ms[~]
which are persistent in solution; hydrolysis
leads to the N,N-dialkylformamides, hydrolysis with DzO
and workup with H 2 0 to the labeled [ D , j - f ~ r m a m i d e s ~ ~ ~ .
Reaction of the lithium monoalkylamide (1 ) with CO under
these conditions (Procedure[31)and subsequent hydrolysis also
affords the N-alkylformamide ( 4 ) [yield based on ( 1 ) cu.
30
but hydrolysis with D 2 0 and workup with H 2 0 leads
to unlabeled ( 4 ) [yield cu. 50 %141]. Analogous carbonylation
of the labeled amide [Dt]-(l )-prepared from labeled terfbutylamide ([D,]-(5), [Dt]-(5), (5)y5', contaminated
with ( I )-and
hydrolysis yields the labeled formamide
x)],
j20,
( 1 2 ) ('?I.
1 1 0 ) . 1 / 3 1 and LIOH. ( 1 8 ) is iiut formed when the solutions
arepouredintoalargeexcessofH,O(PR, hydrolysis): it isalso not formed
in method (C). r-iu addition of ( 1 2 ) to (13). Thus ( 1 8 ) is neither
derived from ( 1 6 ) . nor from a dimer ( 2 0 ) of ( 1 2 ) .
Two further, not fully identified compounds are found m the hydrolysate
of the solution containing ( 3 ) .
Without furthet- passage of C O , the C O still present in the solution
reacts alowly with ( J I ) and ( I ? ) on standing for 20-48h
at c i i .
-7S"C (yield of ( 1 3 ) after hydrolysis mi. 20S;. of ( 1 4 ) 20--40",,
[7a]: hydrolysia with D 2 0 give5 [ D l ] - ( / 3 ) : (13) - 9 7 : 3 ) . We d o not
know whether the carbonylations under thcse conditions are reversible,
as is the case at elevated temperatures: J . C. Powrrs, R. Siiridrr. 7:
G Pciv~wit*.Tetrahedron Lett. 1965. 1713.
SO- 80"; [ D l ] - f / 4 ) severalruns,50-20'YU ( 1 4 ) : [Di]-(14) apparently
undcrgoes partial H/D exchange during isolation.
With T H F alone a jdly is formed which is converted into a normal
solution by addition of DME.
[Dl]-(4) (91 2,) and a small amount of ( 4 ) ( 9 % ; yield of
[D,]-(4) + ( 4 ) c a . 15x1".51).Theratios[Dt]-(l ):( I )and [D2](5):[Di]-(5):(5) were not determined independently,
because D/H exchange is difficult to avoid during manipulation and analysis; [Dl]-( I ) ; ( I ) can at best have been
2 96:4''] and may have dropped to 2 91 :9 by D/H exchange.
These experiments alone afford proof-which is more convincing when contrasted with the corresponding experiments with
authentic carbamoyllithium~~~~-that(2) and [D11( 2 ) are shortlived primary products and rearrange to give
(3) and [Dt]-(3). respectively. This result can be generalized as formulated in the title. The derivatives described
in 1'1 therefore did not have structures of type ( 6 ) most
likely are the structures of type ( 7)15'.
Carbonylation of Lithium Monoalkylamides to Give
N-Lithio(alky1)formamides
By Vulentin Rautenstruuch and Michel Joyeux[*]
We report that the carbamoyllithium ( 2 ) which formed when
carbon monoxide is passed into solutions of lithium teri-butyl-_
~-
[*] Dr V. Rautenstrduch ['I, Dr. M. Joyeux
Firnienich SA. Laboratoire de Recherche
b. p. 239, CH- I 2 I I Geneve 8 (Switzerland)
['I Author to whom correspondence should be addressed; on ieavc at the
Department of Chemistry. Stanford University, Standford, Calif. 94305
(USA).
Received: May 22, 1978 [ Z 72b IT:]
German version: Angew. C'hem. Y I . 73 (1979)
P. J u t t . F. W Sihr6der, Angew. Chem. 83, 334 (1971); Angew. Chein.
Int. Ed. Engl. 1 0 , 339 (1971).
[ 2 ] pK, of R z N C H O ( a . 38 ( R . R. Fru,wr. P. R. Huhrrt, Can. J . Chern.
j Z . 185 (1974)), of R N H C H O ( u . I 8 ( J . Z . 2ohicX.i.. The Chemistry
of Aniides. Wiley-lntcrscience. New York 1970, p. I C - . 197).
[3] V Routrnsri.aurh. M . J O Y E U S Angew.
,
Chem. 9 1 , 7 2 (1979); Angew.
Chem. Int. Ed. Engl. J X , 83 (19791.
[4] The variations in the yields arc probably caused by variations i n the
CO flou. b j incomplete extraction, and i n the case of [ D , ] - f I )
hy inaccurate weighing of([D,J-/5), [Di]-C5,, f 5 ) [ 5 ] ) .
[l]
85
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