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Formation of Indirubin and 2-Ethoxy-3-(indol-2-yl)indole from 2-Ethoxyindole.

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Phenyl isocyanate ( I 1.9 g) is added dropwise to a stirred
solution of 13.8 g of N-isobutenylpiperidine and 10.8 g of
cyclohexyl isonitrile in 25 ml of dimethylformamide. The
temperature rises to 33°C. The mixture is then heated to
50°C for 30 min. On cooling, 33 g of the title compound
crystallizes out; after recrystallization from acetonitrile it
melts at 95-97 "C.
2-(t-Butylimino) -I -(p-chlorophen~.IJ-4,4-dim~~thyl3-pyrrolidino-5-pyrrolidone
When 12.5 g of N-isobutenylpyrrolidine, 8.3 g of t-butyl
isonitrile, and 15.4 g of p-chlorophenyl isocyanate are dissolved in 40 ml of dimethylformamide, the temperature rises to
62'C. On cooling, 30 g of the title compound crystallizes
out; after recrystallization from acetonitrile, the m.p. is
84-85 OC.
p-Toluenesulfonyl isocyanate (19.7 g) is added dropwise to a
solution of 12.5 g of N-isobutenylpyrrolidine and 10.8 g of
cyclohexyl isonitrile in 60 ml of acetonitrile, the temperature
rising to 65OC. On cooling, 40 g of title compound is deposited; after recrystallization from acetonitrile, the m.p. is
110-1 13 "C.
4,4-Dimethyl-2-(2-niethyl-3-nitrophenylimino)I -phenyl-3-pyrrolidino-S-pyrrolidone
Phenyl isocyanate (23.8 g) is added dropwise to 25.0 g of
N-isobutenylpyrrolidine and 32.4 g of 6-methyl-3-nitrophenyl isonitrile in 100 ml of acetonitrile, the solution being
cooled to keep the temperature below 6OoC. On cooling,
65 g of the title compound precipitates as orange-yellow
crystals, which after recrystallization from acetonitrile melt
at 164-165OC.
I - Cyclohexyl-2-cyclohexyiimino-4,4-dimethyl3-pyrrolidino-5-thiopyrrolidone:
Twenty-five grams of N-isobutenylpyrrolidine, 28.2 g of
cyclohexyl isothiocyanate, and 20.6 g of cyclohexyl isonitrile
are heated together in 100 ml of dimethylformamide for 3 h
at 120 "C. On cooling, 68 g of colorless crystals separate out,
m. p. 76-77 OC from ethanol.
2-Cyclohexylimino-4,4-dimethyl1-(p-nitrophenyl) -
A solution of 36 g of g-nitrophenyl isothiocyanate, 20.6 g of
cyclohexyl isonitrile, and 28.0 g of N-isobutenylpiperidine in
100 ml of acetonitrile is refluxed for 1 h. On cooling, 77 g
of bright yellow crystals are deposited, m . p . 119-120°C
from ethanol.
2-Cyclohexylimino-3-pyrro~idin~1,4,4-trimethyI5-thiopyrrolidine :
A solution of 25 g of N-isobutenylpyrrolidine, 14.6 g of
methyl isothiocyanate, and 20.6 g of cyclohexyl isonitrile in
50 ml of acetonitrile is refluxed for 6 h. On cooling, 42 g of
title compound is deposited, m.p. 97-98 "C from ethanol.
4,4- Dimethyl-2-(3,3'-dirnethyl-4-crzophenylimino)
I -(p-nitrophenyl) -3-piperidino-5-thiopyrrolidone
A solution of 47 g of 3,3'-dimethyl-4-isocyanoazobenzene,
36 g of p-nitrophenyl isothiocyanate, and 28 g of N-isobutenylpiperidine in 300 ml of acetonitrile is refluxed for 3 h.
On cooling, 85 g of orange-yellow crystals are obtained,
m.p. 141-142°C from ethanol.
If diaminodienes, di-isocyanates, or di-isothiocyanates are
used as starting materials, the corresponding bicyclic heterocycles are obtained. The reaction has grest scope.
Received: February 4th, 1965
[ Z 942/768 I € ]
Publication deferred until n o w at the authors' request
German version: Angew. Chem. 77, 544 (1965)
[ I ] Multicomponent Reactions, Part 2.
Part 1: K . Ley and
R . Nnst, Angew. Chem. 77, 544 (1965); Angew. Chem. internat.
Edit. 4, 519 (1965).
Synthesis of 2-Imino-Cthioxo-1,3-diazetidine
Derivatives by Cycloaddition of Isothiocyanates
onto Carbodiimides
By Dr. H. Ulrich and Dr. A. A. R. Sayigh
The Upjohn Company, Carwin Research Laboratories,
North Haven, Connecticut (U.S.A.)
The addition of isothiocyanates onto carbodiimides has not
yet been observed. We found that 2-imino-4-thioxo-1,3diazetidines (i) are formed in quantitative yields when isothiocyanates activated by an electron-withdrawing substituent
(such as p-nitrophenyl or alkyl- and arylsulfonyl) and
carbodiimides are mixed at room temperature in a molar
ratio of 1 : 1 with or without solvent. The reaction can be
followed by infrared spectroscopy by the disappearance
of the absorptions in the cumulative double bond region
(4.7-4.9 p) and by the appearance of a new C = N
absorption a t 6.05 {J. in the case of ( I n ) and ( I b ) , at
6.19 p in the case of ( I c ) , and at 6.25 p in the case of (Id).
(((I), R
ib), R
(el, R
(dJ, R
m.p. 51-52°C
m.p. 73-75 "C
m.p. 173-174 "C
m.p. 128-129°C
The structure of the compounds ( I ) was determined by
elemental analysis, molecular weight determination and
cleavage into the starting components o n heating in an inert
solvent (o-dichlorobenzene, 180 "C). In no instance was
cleavage with formation of the unsymmetrically substituted
carbodiimide observed. With compounds ( l c ) and ( I d ) ,
especially, such a reaction would have been detected easily
since sulfonyl isothiocyanates absorb at 5.25 p, while other
isothiocyanates absorb at 4.9 p.
Received: March 26th, 1965
[Z 951/774 LEI
German version: Angew. Chem. 77, 545 (1965)
Formation of Indirubin and 2-Ethoxy-3(indol-2-y1)indole from 2-Ethoxyindole
By Prof. Dr. H. Plieninger, Dr. U. Lerch, and
Dipl.-Chem. D. Wild
Organisch-Chemisches Institut
der Universitat Heidelberg (Germany)
2-Ethoxyindole (IJ [ I ] in solution or in the solid state turns
red-violet on admission of oxygen. After a crystalline sample
of (I) has stood for several weeks in air, unchanged starting
material can be extracted with ether or ethanol, and the
undissolved residue of pigment can be recrystallized from
acetic acid/ethanol. The melting point, infrared spectrum,
Angew. Chem. inlernat. Edit.
Vol. 4 (1965) / No.6
and behavior on thin-layer chromatograms of the colored
product are those of indirubin (2)
Pd(PF3)d is thermally less stable than Pt(PF3)4. It is also a
colorless, mobile liquid and melts at -41 O C . Decomposition
occurs above -2OOC with deposition of a palladium mirror.
Rapid decomposition with PF3 literally boiling off occurs at
room temperature. The infrared spectrum of the compound
was therefore measured at -25 O C between KCI plates [4];
the two P-F valence vibration frequencies expected for a
tetrahedral structure were found at 910 (vs, b) and 860 (s)
Received: April 5th, 1965
[Z 956/783 IE]
German version: Angew. Chem. 77, 505 (1965)
H H 5 C ,I A . 0
IXth communication on metal trifluorophosphine complexes.
VIlIth communication: Th. Kruck and K . Baur, Chem. Ber.
98 (1965), in the press.
[2] Th. Kruck, W . Lang, and A . Engelmann, Angew. Chem. 77,
132 (1965); Angew. Chem. internat. Edit. 4, 148 (1965), and
literature cited there.
[3] The infrared spectra were obtained using a Perkin-Elmer
Model 21 spectrophotometer with NaCl optics. s = strong,
vs very strong, b - broad.
[4] Gas-phase measurements at room temperature reveal only
the v p - ~vibration bands at 892 and 853 cm-1 of the liberated
PF3, together with an intense broad band at 865 cm-1, which is
ascribed to an as yet unidentified decomposition product.
A similar "dimerization" is observed o n treating 2-ethoxyindole in dioxane at 2OoC with boron trifluoride etherate.
A BF3 complex is deposited from which colorless 2-ethoxy-3(indol-2-y1)indoIe ( 3 ) is formed on adding aqueous ammonia. The structure of ( 3 ) was proved by its elemental
analysis, infrared spectrum (two N H absorptions at 3440 and
3380 cm-I), and N M R spectrum [signals at 1.16 7 (NH),
2.1-2.9 T (multiplet; aromatic protons and 1 NH), 3.16 T
(singlet; $proton), 5.86 T (quartet), and 8.62 T (triplet) in
area ratios of 1 :9: 1 : 2: 31. Compound (3) gives a deep blue
color in the Ehrlich reaction and is oxidized in air. Indirubin
(2) could be isolated from the oxidation products.
The introductory step in both reactions is possibly an
electrophilic attack [by oxygen in the autoxidation to (2)
and by BF, during the formation of ( 3 ) ] at C-3 of the ethoxyindole skeleton.
[Z 950/776 IE]
Received: February 25th, 1965; supplemented: March 30th, 1965
German version: Angew. Chem. 77, 505 (1965)
[ I ] H . Plieninger and H . Bauer, Angew. Chem. 73, 433 (1961).
Synthesis of Bis(diaziridin-1-ylmethy1ene)hydrazine
By Doz. Dr. R. Neidlein and W. Haussmann
lnstitut fur Pharmazeutische Chemie und Lebensmittelchemie
der Universitat Marburg (Germany)
Starting fiom isocyanogen tetrabromide ( I ) [l, 21, which
can be regarded as a derivative of the (as yet unknown) isocyanogen, we have synthesized various tetra-amino derivatives of isocyanogen.
.. .. ,Br
C = N- N= C\
Synthesis of Tetrakis(trifluorophosphine)platinum(0) and Tetrakis(trifluoroph0sphine)palladium(0) [1]
By Priv.-Doz. Dr. Th. Kruck and Dipl.-Chem. K. Baur
Anorganisch-Chemisches Laboratorium der
Technischen Hochschule Munchen (Germany)
The reductive fluorophosphination of simple transition metal
salts has proved to be a generally applicable method of
preparing metal trifluorophosphines, which are largely
analogous to the metal carbonyls [ I , 21.
Ontreating anhydrous platinum(1I) chlorideand palladium(I1)
chloride with trifluorophosphine in the presence of copper
powder as halogen acceptor at 100 "C and initial PF3 pressures
of 300 atm (with PdC12) or 100 atm (for PtCIz), the tetrakis(trifluorophosphine) derivatives of the two platinum metals
and 80
are formed. The yields are 70-80 :()
These volatile, hydrophobic compounds deserve attention,
since volatile, four-coordinate complexes, including carbonyls,
of these metals in the zerovalent state had previously not been
known. I n appearance and other properties the new compounds resemble nickel trifluorophosphine and nickel
Pt(PF3)4 is a colorless, mobile liquid with m.p. -15 " C ,
b. p. 86 'C/730 mm, which decomposes above 90 "C with deposition of the metal. In a nitrogen atmosphere the liquid can
be distilled at normal pressure with only little decomposition.
The pale yellow distillate must however be recondensed in
vacuum at 20 "C t o render it colorless and analytically pure.
In the infrared spectrum [3] of the diamagnetic compound,
only two P-F valence vibration bands are observed, a 3 with
Ni(PF.3)4, namely at 906 (vs) and 867 cm-i (vs) (gas-phase
measurement), which indicate a tetrahedral structure (Td).
Anpew. Chem. intermit. Edit. / Val. 4 (1965) / No. 6
Bis(diaziridin-1-ylmethy1ene)hydrazine (2) is prepared by
dissolving 3.71 g (0.01 mole) of isocyanogen tetrabromide
( I ) in 20 ml of anhydrous tetrahydrofuran, adding 1.6 g
(0,04 mole) of finely powdered sodium hydroxide, cooling in
ice, and adding 3.44 g (0.08 mole) of ethyleneimine dropwise
with vigorous stirring. Stirring is continued for 2 h at room
temperature. After filtering off the KBr and distilling the
tetrahydrofuran from the filtrate, a colorless oil remains,
which crystallizes on standing in a refrigerator for several
m.p. 134-135 "C.
days; yield 1.5 g (68
Bis(dipiperidinomethy1ene)hydrazine is prepared analogously;
m.p. 148.5 "C.
yield 2.9 g (76
The compound (2) is very sensitive t o acids, of which even
traces cause an explosion-like polymerization.
Received: April 7th, 1965
[Z 9591785 E l
German version: Angew. Chem. 77, 506 (1965)
[ I ] J. Thiele, Liebigs Ann. Chem. 303, 57 (1898).
[2] J. Diekmann, J. org. Chemistry 28, 2933 (1963).
Synthesis of N-(Alkylthiohalogenomethyiene)
By Doz. Dr. R. Neidlein and W. Haussmann
Institut fur Pharmazeutische Chemie
und Lebensmittelchemie der Universitlt Marburg (Germany)
N-Dichloromethylene sulfonaniides ( I ) [ I ,2] are obtained
by the action of elemental chlorine on S,S-dialkyl-N-sulfonyldithiocarbonimides(2) [3,4] in boiling carbon tetrachloride.
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formation, ethoxy, indole, indirubin, ethoxyindole
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