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Coupling of Diazonium Salts with Enol Ethers.

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Thus, for example, methyl opsopyrrolecarboxylate (9) was
obtained from the readily available ethoxypyrrole ester (8).
In the past, the adducts ( I ) initially formed have been secured
in only a few cases [2]. We have isolated these adducts ( I ) in
almost quantitative yields by reaction of substituted phosphines with tosyl azide. The adducts are lemon-yellow compounds (3u) or (3b) which tlccompose at 88 OC (X = C6H5),
2-Ethoxyindole [ I ] can also be converted into indole with
di borane.
Received, June 25th, 1963
[ Z 530/349 IE]
80 "C (X= N H C G H ~ and
) , 72 "C (X = N(C3H7)z). The linear
structure of the (I-tosyltriazcn-3-y1idcne)phosphoranes(30)
is in accordance with infraretl spectroscopicdl studies of the
P=N stretching frequency [3]. Despite its strong resemblance
t o the spectra of comparablc N-tosylphosphine imides [(2),
R = Ts], the customary coupling with the asymmetric SO2
vibration is lacking in the spectrum of (3u) on account of
the greater distance between Ihe P - N and SO2 proups [4].
No diazo band corresponding to (3h) appears in either the
double or triple bond region.
N,N-Bis(diphenylphosphino)anilinc H.jCs-N[P(C&l5)& reacts with two moles of tosyl azide to give the golden-yellow
bis-[(l-tosyltriazen-3-ylidene)~~hosphoranyl]an~l~ne
(4) which
decomposes at 103 OC and contains thirteen atoms of Group
V and VI elements in a row.
German version: Angew. Chem. 75, 724 (1963).
[I] H . Plieninger, H . Bauev, and .4. Katritzky, Liebigs Ann. Chem.
654, 165 (1962).
Coupling of Diazonium Salts with Enol Ethers
By Dr. M . Secfelder and Dr. H. Eilingsfeld
Farbenforschungslaboratorium der Badischen Anilin- &
Soda-Fabrik AG, Ludwigshafen am Rhein (Germany)
Diazonium salts ( I ) couple with enol ethers (2) to give
monoarylhydrazones of 1,2-dicarbonyl compounds ( 3 ) .
~
0
I'h
I'll
0
II,C-C'~;H,-S-N=N-N=P-N--PI=N-N=N-~--C~I~,-('I~,
II--I - I --_I1
II
I
0
1'11
l
l
Ph Ph
4
P h = (',$I5
(4)
These monoarylhydrazones ( 3 ) can be converted with p-nitrophenylhydrazine into osazones.
p-Nitrophenyldiazonium chloride or fluoroborate couple
with vinyl ethyl ether (R = R' = H, R" = C2H5) in water at
0-10°C to give a-(p-nitropheny1hydrazono)acetaldehyde
(m.p. 188- 190 'C, decomp.); with p-nitrophenylhydrazine,
this is converted into I ,2-di-(p-nitrophenylhydrazono)ethane
(n1.p. 310"C, 311 "C [l]). Ethyl propenyl ether (R = CH3,
R' = H, R" == C2H5) and ethyl isopropenyl ether (R = H,
R' = CH3, R" = C2H5) couple to give isomeric p-nitrophenylhydrazonopropanones, which react further with
p-nitrophenylhydrazine to give 2,3-di-(p-nitrophenyIhydrazono)propane (m.p. 270 "C, 276-277 "C [2]).
Dihydrofuran reacts with p-nitrophenyldiazonium salts,
yielding 2-(p-nitrophenylhydrazono)-4-hydroxybutyraldehyde
(m.p. 118 -12OoC, decomp.).
Received, June 28th, 1963
[Z 532/356 IE]
German version: Angew. Chem. 75, 724 (1963).
[I] A . Wohl and C. Neuberg, Ber. dtsch. chern. Ges. 33, 3107
(1900).
[Z] V. Wov, Chem. Ber. 86, 843 (1953).
Stable Primary Adducts from the Staudinger
Reaction
By Dr. H. Bock and Dipl.-Chem. W. Wiegrabe [I]
Received. .luly 1st. 1963
[Z 534/357 IE]
German vcrsion: Angew. Chem. 75, 790 (1963).
[l] Communication No. 2 on Invcstigations of thc Reactivity of
the P-N Double Bond. Communication No. I : H . Bock and
W. Wiegrube, Angew. Chem. 74, 327 (1962); Angew. Chem.
internat. Edit. I , 265 (1962).
[2] H . Staudiriger and J . M c y w , Helv. chim. Acta 2, 635 (1919);
E. Bergmann and H . A . Wolf, Bcr. dtsch. chem. Ges. 360, 1176
(1930); L. Horner and A . Gross, Liebigs Ann. Chem. 591, 117
(1955); G. Wifrig and K . Schwmpzenbarh, Liebigs Ann. Chem. 650,
1 (1961); J. E. Lefffer, 11. Hon,rheq, Y . Tsuno, and J . Forshlad,
J. org. Chemistry 26, 48 10 (1 90 I).
[3] W.Bock and W . Wiegrubc, unpublished data.
141 T. MoeIler and A . Vandi,.I. org. Chemistry 27, 3511 (1962).
Relationships between the Color and Constitution
of Azophosphonic Acid Derivatives
By Dr. H. Bock, Dr. E. Baltin, and Dr. G. Rudolph [I]
Institut fur Anorganische Chcmic der Universitiit Miinchen
(G ermdn y)
Azodiphosphonic acid derivatives ( I ) are violet, phenylazophosphonic acid derivatives (2) are red.
0
0
0
Y, P-N=
y,
II
N -P<
I' Y
@=N-PCY
II y
lnstitut fur Anorganische Chemie der Universitiit Munchen
(Germany)
Studies o n the reactivity of the P=N double bond led to the
synthesis of numerous N-alkyl-, N-aryl-, and N-tosyl-phosphine imides (2) by the Staudinger reaction of phosphine
derivatives with azides.
The unexpected color of thcsc x-systems of limited size corresponds to a considerable bathochromatic shift of the lowintensity n +TC* transition of the azo group in the visible
region (for comparison : azomethane 29000; the azodicarboxylic anion 25000; azobenxne 22750; the phenylazophosphonic anion 20700;the azodiphosphonic anion 18800 cm-1).
Variation of Y causes shifts in the long-wave absorption
maximum in ( I ) and (2) with approximately constant differences in wave number (Avmax ( 2 ) - ( 1 ) = 2000 cm-1) and
NR2 > OR > Oo.
hypsochromic in the order ('sH5
-
484
Angew. Chem. iirtrrwat.
Edit. I Vol. 2 (1963) I No. 8
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