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Detection of Open-Chain Intermediates in the Formation of -Lactams from Ketenes and Azomethines.

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[7] J. Ficini and C . Barbara, Tetrahedron Letters 1966, 6425.
I81 Three further compounds of this type ("ethynologous amides
and urethanes") were prepared similarly but independently of us
by K . H N f w r and M . Neuenschwander, Angew. Chem. 80, 443
(1968); Angew. Chem. internat. Edit. 7, 459 (1968). - The diethylamide of (diethy1amino)propiolic acid was obtained by a
different route by H. C. Viehe and R. Buyle (personal communication from H . G. Viefie).
19) R . D . Chambers, H . D . Clark, L. W . Reeves, and C . J . Wiiiis,
Canad. J . Chem. 39, 258 (1961).
[lo] We thank Dr. A. Prox for analysis of the mass spectrum of
compound (7).
Tris(o-arylenedioxo)- and Bis(o-arylenedioxo)organosilicic Acids Containing
Hexacoordinated and Pentacoordinated Silicon
By H. Meyer, G. Nagorsen, and A . WeissC*l
The reaction of molten pyrocatechol with halogenosilanes
under nitrogen leads t o the formation of complex o-phenylenedioxosilicic acids containing hexacoordinated and pentacoordinated silicon:
trichlorosilane. Yield without reprecipitation: 13 g (82 %) of
( 2 a ) or 8.8 g (68
of ( 2 b ) .
x)
Received: August 8, I968
[Z 858 IE]
German version: Angew. Chem. 80,849 (1968)
[ * ] Dipl.-Chem. H. Meyer, Dr.G. Nagorsen and Prof. Dr.A. WeiR
lnstitut fur anorganische Chemie der Universitat
8 Munchen 2, Meiserstrasse 1 (Germany)
[l] A. Rosenheim, B. Reibmann, and G. Schendei, 2. anorg. allg.
Chem. 196, 160 (1931).
[2] Salts of the pentacoordinated acid have already been prepared: C . A . Frye, J. Amer. chem. SOC.86, 3170 (1964).
Detection of Open-Chain Intermediates in the
Formation of P-Lactams from Ketenes and
Azomethines
By R . Huisgen, B. A . Davis. and M. Morikawa[*J
P-Lactams were first obtained by Staudinger on cycloaddition
of ketenes t o N-aralkylidene-arylamines [ I 21. Other types of
azomethines as well as heteroaromatic bases preferentially
formed adducts with two equivalents of dimethylketene [31,
which have recently been found to be hydrogenated 2-methylene-1,3-oxazin-6-ones 1 4 ~ 5 1 .
We observed that in the system diphenylketene ( I ) + benzylidenemethylamine (21, the 1:l adduct ( 4 ) or the 2 : l adduct
( 5 ) is preferentially formed according to the reaction conditions. We therefore conclude that a common intermediate
(3) is involved.
When 10.5 mmole of ( 1 ) in 15 ml of acetonitrile were added
dropwise to a solution of 135 mmole of (2) in 85 ml of
acetonitrile at room temperature, the rapid disappearance of
the yellow ketene color showed that the ketene was quickly
consumed. After removal of the excess of ( 2 ) by high-vacuum
distillation, the N M R analysis indicated 82% of the
lactam ( 4 ) together with 6 % of the 2: 1 adduct ( 5 ) .
On the other hand, when 6.8 mmole of (2) in 35 ml of acetonitrile were added dropwise to 55 mmole of ( I ) in 50 ml of
acetonitrile, the yields were 81 of the 7,3-oxazinone derivative ( 5 ) and 19% of (4)161. When these two procedures were
carried out in benzene with the same proportions, 71 % of
( 4 ) + 1 7 % of ( 5 ) were obtained in the first case and 95 % of
( 5 ) in the second.
9
Other o-dihydroxyarenes, such as 2,3-dihydroxynaphthalene,
can react similarly.
T h e structure of tris(o-pheny1enedioxo)silicic acid ( I ) is
found from the molecular weight (370; cryoscopically in
camphor) and the 'H-NMR spectrum, which contains 2
singlets at T = 3.08 and 4.14 (in DCCI3; T M S as external
standard; the acid protons appear a t T = 4.14), and so indicates that the three pyrocatechol residues are equivalent.
( I ) differs characteristically in its 1H-NMR spectrum from
the product first obtained by Rosenheim et al. 111 from Sic14
and pyrocatechol in ether; the latter product gives three
signals at T = 2.85, 3.14, and 7.68 (in DCCl3; TMS as external
standard). ( I ) is dibasic, appears t o be trimeric in benzene as
a result of hydrogen bonding, and reacts with 2 moles of
alkylamine to form a salt.
The IH-NMR spectra of bis(o-pheny1enedioxo)methyl- and (C&,)zC=C=O
bis(o-pheny1enedioxo)phenylsilicicacids, (2a) and (2b), show (1) +
that the two pyrocatechol residues are again equivalent in
these cases. These compounds also form salts with alkyl- C6H5-CH=N-CH3
amines[21. Powder diagrams show that (1) and (2), unlike
(2)
the alkylammonium salts, are amorphous.
P-
0
(c6H5)2c+c@
e
'0
H CI + N ~ C H 3
I
(3)
Procedure:
Preparation of ( I ) :
6.6 g (60 mmole) of pyrocatechol are melted under dry nitrogen. 3.4 g (20 mmole) of silicon tetrachloride are added dropwise t o the melt with vigorous stirring at a bath temperature
of 14OOC and over a period of 30 minutes. After a further
30 minutes, unreacted pyrocatechol and other volatile components are removed at = 12O"CjlO-2 torr. After cooling,
the residue is dissolved in the minimum quantity of boiling
absolute benzene and (1) is precipitated with absolute petroleum ether. Removal of the remaining solvent at 100 'C/10-2
torr leaves a red, vitreous mass that is sensitive t o moisture.
YieId = 4 g (57%).
Preparation of ( 2 ) :
11 g (0.1 mole) of pyrocatechol are reacted as described
above with 10.6 g (0.05 mole) of freshly distilled phenyltrichloro-silane or 7.74 g (0.05 mole) of freshly distilled methyl-
826
(4)
(5)
The p-lactam ( 4 ) did not form the 2: 1 adduct ( 5 ) with excess
diphenylketene ( I ) even after 6 hours at 14O0C. Thus the
above reactions evidently involved a n open-chain intermediate, presumably the 1,4-dipole (3) 171, which either
closes the lactam ring or undergoes cycloaddition with a
second molecule of diphenylketene to form ( 5 ) .
( I ) and isoquinoline in ether at 2OoC gave 89% of a 2:l
adduct, which we assume to have the formula (7), by analogy
with the dimethylketene-quinoline adduct 151. On the other
hand, when isoquinoline and excess phenyl isocyanate were
dissolved in benzene (the components d o not react with each
other in the cold) and diphenylketene slowly added, 30 % of
Angew. Chem. internat. Edit.
/ Vol. 7 (1968)/ N o . I0
~
\
o
~
c
c.:
(
c
6
$./@
6%
%
)
+ C,H,-N=C=O
2
q
0
(C6II5)2
sodium methoxide/methanol or ( 9 ) and diazomethane gave
the methyl" ester (10): m.p. = 142-143 "C, C = O 1650 and
1730 cm-1; N M R (CDC13) T = 7.21 (NCHS), S;6.43 (OCHd,
S; 5.09 (benzhydryl H ) , S. (7): 93% yield, m.p. = 146 to
148 "C, C - 0 and C-C 1635 and 1758 cm-1; N M R (CDC13):
2
-.---I
+ (C,H,),C=C=o
y y c(c
1
NJc6H5)2
0
IBa)
0
I 71
0
N
C6H;
~ N y C ( C & ) ~
C6H;N)fo
0
(86)
the 1: I : 1 adduct ( 8 ) were isolated [8J [**I. Thus the second
ketene molecule can be replaced in its role as the dipola
rophile and the intermediate 1,4-dipole (6) is intercepted by
phenyl isocyanate.
Gonzes and JoulliC 191 recently reacted benzylideneaniline
with ketene in SO2 and obtained a thiazolidone 1,l-dioxide
stoppas a five-membered cycloadduct. Kagan and Luche
ed the reaction of (1)with benzylideneaniline by the addition
of methanol. and isolated 10% of a n open-chain methanol
adduct of the 1,4-dipole.
Properties and proof of structures of new compounds[lll:
l-Meth~l-3.3,4-tri~hen~l-2-azetidinone
( 4 ) , m.p. = 118 O C ,
c = o 1752cm-l; N M R (CDC13*6o MHz): = 7.17 (CH3)*
S;4.73 (tert.H), S.3-Methyl-4,5,5-triphenyl-2-diphenylmethy( 5 ):m.p. = 208-209 *c(dec.1,
leneperhydro-1,3-oxazin-6-one
C = O and C = C 1757 and 1630 cm-1; N M R (CDCI3): 7 = 7.67
(CH3), s; 5.08 ( f e r t . H ) , s. When shortly boiled in 80%
dioxane, ( 5 ) was converted into ( 9 ) : m.p. = 201-203 "C,
amide-1 1616, acid c-0 1727 cm-'. ( 9 ) is insoluble in
aqueous sodium hydroxide solution, but can be titrated in
dimethyl sulfoxide with NaOH.
N M R (CD3SOCW: T =17.31 (CH3), s.The singlet at T = 4.82
corresponds to the benzhydryl proton, since this signal is
absent in the case of the Product from ( 5 ) + D2O; the signal
of the second tert.H lies below the phenyl signals. ( 5 ) and
4.98 (tert.H), S. (7) does not react with aqueous dioxane;
it is hydrolyzed by dioxanejaqueous hydrochloric acid to
give diphenylacetic acid and isoquinoline.
T=
Received: July 31, 1968
[Z 859 IE]
German version: Angew. Chem. 80, 802 (1968)
[*I Prof. Dr. R. Huisgen
Institut fur Organische Chemie der Universitst
8 Munchen 2, Karlstrasse 23 (Germany)
Dr. B. A. Davis (A.-v.-Humboldt Fellow, 1967)
University Chemical Laboratory
Lensfield Road, Cambridge (England)
Dr. M. Morikawa
Toyo Rayon Co., Ltd.
Sonoyama 3, Otsu (Japan)
H . Stnuclinger, Liebigs Ann. Chem, 356, 51 (1907).
121 Review: J. C. Sheehan and E. J. Corey, Org. Reactions 9, 388
(1957).
[3] H . Srrrudingerand H . W. Klever, Ber, dtsch, (-hem. Ges. 39,
968 (1906); H . Staudinger, H. W. Klever, and P . Kober, Liebigs
Ann. Chem. 374, 1 (1910).
[4] J . C.Martin, V . A . Hoyle, and K . C. Brannock, Tetrahedron
Letters 1965, 3589.
[5] R . N . Pratt, G . A . Taylor, and S . A . Proctor, J. &em. Soc.
(London) C 1967, 1569.
[6] Yields based on the reactant present in the smaller quantity.
[71 For definition see: R . Hujsgen and K . Herbig, Liebigs Ann,
Chem. 688, 98 (1965); R. Huisgen, M . Morikawa, K. Herbig, and
E. Brunn, Chem. Ber. 100, 1094 (1967).
[8] R . Huisgen, K . Herbig, and M. Morikawa, Chem. Ber. 100,
1107 (1967).
[**I It is not yet certain whether this is (8a) or (86). No decision
can be reached from the IR and NMR spectra.
[9] A . Comes and M . M . Joullid, Chem. Commun. 1967, 935.
[lo] H . B. Kagan and J. L . Luche, Tetrahedron Letters 1968,
3093.
[11] Correct elementary analyses and molecular weight determinations have been carried out for all the new compounds.
C O N F E R E N C E REPORTS
Preparation and Properties of the Diastereoisomeric 1,3,5-Triglycidyl-s-triazinetriones
By M. Budnowski[*]
Interaction of epichlorohydrin ( 2 ) and cyanuric acid ( I )
above 60 "C leads to the N-alkyl compounds ( 3 ) in a thermodynamically controlled reaction. A relatively small excess of
(2) favors formation of the addition product ( 3 ~ 1whereas
,
a
large excess converts (3c) to the desired (3f). Thus epichlorohydrin functions as both alkylating agent and base. The
intermediates (3dl and ( 3 e ) were detected by thin-layer
chromatography.
Fractional crystallization of the product ( 3 f ) gives two
stereoisomers a-(3f) and p-(3f), which were considered, o n
Angew. Chem. internat. Edit.
Vol. 7 (1968)/ No. 10
account of the chirality of the glycidyl group, toebe'racernates
with the configurations (R,R,R/S,S,S) or (R,R,S/S,S,R)
[m.p. 105 "C(a), 156 "C(P)].
In order to assign configurations to a-(3f) and @-(3f)and to
the products therefrom suitable additive and degradative
reactions were performed.
Among reagents of the type HCA- used for addition, 0Aryl, S-Aryl, S-Alkyl, and NR2 act as anions. Treatment
with aequeous alkali leads to partial or total hydrolysis.
The adduct ( 4 ) is formed in almost quantitative yield on
addition of 3 moles of H A to 1 mole of (3f). Presence of a
base leads, again almost quantitatively, to the oxazolidone
(51, which is also accessible by heating ( 4 ) with bases. The
isomers or-(3f) and p-(3f) yield different adducts ( 4 ) but the
same oxazolidone ( 5 ) .
827
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open, azomethines, chains, detection, formation, ketene, intermediate, lactam
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