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Benzo[a]quinolizinium Salts from 3 4-Dihydroxyphenethylamine Hydrobromide and Acetoacetaldehyde a Possibly Biogenetic-Type Cyclization.

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triaza-2,5-diborolidine (2), R2 =. C6H5, R3 = CH3, b.p.
180-182"C/3 mm, m.p. 106-108°C (sealed tube, uncorrected), precipitates out on cooling. Concentration of the
mother liquor yields a second crop of crystals; the overall
yield is about 85 %.
appear to be stable to heat.
For example, when (2), R2 = C6H5, R3 = CH3, is heated to
225 'C in vncuu, no signs of decomposition are found. This
behavior seems to indicate the existence of resonance stabilization of the ring by participation of BN double bonds.
This assumption is supported by the presence of a peak in
the infrared spectrum of (2) near 1400 cm-1; this region is
normally assigned to BN double bonds [3]. In addition, the
chemical reactions of (2), e.g. with metal carbonyls, indicate
a strong similarity between triazadiborolidines and the
cyclopentadiene system.
However, the heterocycle (2) is not stable t o hydrolysis.
Traces of moisture first attack the B-N-B bridge to yield
202-204 "C [4]; this is followed by ring cleavage to afford
dihydroxyphenylborane and N,N'-dimethylhydrazine.
Received, April 2nd and 27th, 1964
[ Z 730/556 IE]
German version: Angew. Chem. 76. 535 (1964)
[ I ] H. Noth and W. Regnef, 2. Naturf. I86, 1138 (1963).
[2] H. Jenne and K . Niedenzu, Inorg. Chem. 3, 68 (1964).
[3] G. M. Wyman, K . Niedenzu, and J. W. Dawson, J. chem. SOC.
(London) 1962,4068.
[4] A melting point of 204 "C is given by [I].
Diethylselenothiophosphinic Acid Derivatives
By Doz. Dr. W. Kuchen and Dip].-Chem. B. Knop
Institut fur Anorganische Chemie und Electrochemie
der Technischen Hochschule Aachen (Germany)
Sodium diethylselenothiophosphinate ( l a ) has been obtained
both in the fused state according to the equation:
(ClHs)>P(S)-P(S) (C2HS)Z
+ NalSe + Se ~--+
2 h
2 (CzH&P(S)SeNa
crystalline product, m.p. 56.5 "C, which is formed in water
by the reaction:
is most probably bis(diethylselenophosphoryl)disulfane, especially since the infrared spectrum of the yellow compound
in the KBr region is practically the same as that of
Diethylselenothiophosphinicesters, e. g. ( C ~ H ~ ) Z P ( S ) S ~ C ~ H %
b.p. 135 "C/lO mm, n'," = 1.5854, and ( C ~ H ~ ) Z P ( S ) S ~ - ~ - C ~ H ~ ,
b.p. 86-87 0C/0.06 mm, n'," = 1.5738, were obtained smoothly
by refluxing (Ib) with alkyl bromides.
(C2Hs)2P(S)SeNa2H 2 0
+ RBr
+ (CZH&P(S)SeR
+ NaBr
The structures proposed for the esters are supported by the
separation of diethylphosphinothioic bromide from the
products of the reaction of any one of them with 1 mole of
bromine, the main reaction probably being the following:
+ Br2 + (C*HS)P(S)Br + RSeBr.
Compound (Ib) reacts with metals t o form non-electrolytic
inner complexes of the type:
( C : , I I ~ ) ~ P hl!n
e. g . bis(diethylselenothiophosphinato)zinc(II), m. p. 157 'C;
-cadmium(lI), m. p. 160O C ; -nickel(Il), olive-green, decomp.
> 142 OC; -lead(II), green-yellow, m.p. 132°C; orange-red
tris(diethylselenothiophosphinato)bismuth(III), m. p. 94 "C.
The zinc and cadmium complexes, like the corresponding
dialkyldithiophosphinato complexes ( 4 ) of these t w o metals,
are associated in benzene [3]. The thermal and chemical
stabilities [3] of the compounds (4) are not attained by their
seleno analogues.
Received, April 13th, 1964
[ Z 726/553 IEI
German version: Angew. Chem. 76, 496 (1964)
[I] W. Kuehen, K . Strolenberg, and J. Metten, Chem. Ber. 96
1733 (1963).
[2] According to M . J. Kabachnik, T. A . Mastrukova, A . E. Shipov, and T . A . Melentyeva, Tetrahedron 9, 10 (1960), the analogous acid (CzH&P(S)OH occurs in aqueous alcoholic solutions
almost completely in the thiono form. The negative charge is
thus, as would be expected, located almost exclusively at the
more electronegative atom.
[3] W. Kuchen and J. Metten, Angew Chem. 72, 584 (1960); W.
Kuchen, J. Metten, and A . Judat, Chem. Ber., in the press.
and in absolute alcohol by the reaction:
It was isolated as its crystalline dihydrate (C2H5)2P(S)SeNa.
2H20 ( I b ) , m.p. 124-125OC. This is isomorphous with
(CzH&P(S)SNa,2HzO [I], which also melts at 124-125 "C.
Aqueous solutions of diethylselenothiophosphinic acid
(C2H&P(S)SeH (2) were obtained from ( I b ) using a
strongly acidic cation exchanger (Ionenaustauscher I, from
E. Merck, Darmstadt, Germany). The acid gradually decomposes on standing for a few hours at room temperature
in diffuse daylight, its solutions turning yellow.
The anion (3) derived from the thiol form of (2) according
to the equilibrium
+ (GH&P(Se)SQ
is presumably practically the only species present in aqueous
solutions of ( I b ) and (2) [2]. Hence the intensely yellow,
Atigsw. Chem. internat. Edit./ Vol. 3 (1964) / NG.7
Benzo[a]quinolizinium Salts from 3,4-Dihydroxyphenethylanline Hydrobromide and Acetoacetaldehyde, a Possibly Biogenetic-Type Cyclization
By Prof. Dr. H. J. Teuber and Dip1.-Chem. D. Laudien
Institut fur Organische Chemie der Universitlt
Frankfurt/Main (Germany)
3,4-Dihydroxyphenethylamine (dopamine) hydrobromide
reacts in hot glacial acetic acid with 2 moles of either acetoacetaldehyde dimethylacetal or l-methoxy-l-buten-3-one,
analogously to tryptamine [l], to yield 40 % of the benzo[a]quinolizinium salt ( I ) and 31 % of the pyridinium salt (2)
[2]. In aqueous solution at 20"C, only about 13 % of (1) is
obtained. Product ( I ) can be separated from (2) as a red
anhydro base C16H15N03.
Pure ( I ) was characterized as its oxime, 2,4-dinitrophenylhydrazone, and diacetyl derivative as well as by the mono-
methyl ether formed on reaction with methyl iodide. On
reduction with sodium borohydride, ( I ) is converted into
the corresponding bright yellow secondary alcohol.
The 60 Mc proton resonance spectrum [3] of the anhydro
base of ( I ) in trifluoroacetic acid (8 = 0 for tetramethylsilane)
shows 4 one-proton singlets at 6 = 9.1, 8.2, 7.7, and 7.1. They
correspond to the isolated protons of the pyridine and benzene
rings and prove that double ring closure has occurred.
This novel synthesis leads in one step beyond the isoquinoline ring closure [4] obtained hitherto with monocarbonyl
compounds to the ring system of protoemetine [5] with
side chains in the "natural" positions.
Received, April 13th, 1964
[Z 7281562 IEl
German version: Anpew. Chem. 76,534 (1964)
[I] H . J. Teuber and U.Hoelimuth, Tetrahedron Letters 1964, 325.
[ 2 ] H. J. Teuber, G . Wenzel, and U. Hochmuth, Chem. Ber. 96,
1119 (1963).
[3] We wish to thank Dr. P. Pfuender for measuring and interpreting the NMR spectra.
[4] C. Schiipf and H. Buyerle, Liebigs Ann. Chem. 513, 190 (1934).
[ 5 ] H.-G. Bait: Ergebnisse der Alkaloid-Chemie bis 1960. Akademie Verlag, Berlin 1961, p. 372.
Other similar etherates are formed by ( I ) , e . g . with di-n- H-14.2 ppm);
butyl ether and with tetrahydrofuran ( ~ G ~ =
the etherate with tetrahydrofuran is soluble in tetrahydrofuran and diethyl ether. After standing for 1-2 days, (2)
dissolves in ether. At the same time, a new N M R signal
appears at about -11 ppm, because the etherate has partly
decomposed into C2H50H and CzH5GeC13. Etherates of
other trihalogenogermanes, e.g. HGe12C1, are formed when
GeIz is dissolved in strong hydrochloric acid/ether
[2(CzH5)z0.HGeIzC1( 3 ) , ~ G - H = -12.1 ppm]. 2(CzH5)20.
HSnC13 ( ~ s , - H = -11.8 ppm) is formed from SnC12 under
the same conditions. The etherates of trihalogenogermanes
differ stronglyin their chemical behavior from the trihalogenogermanes themselves: the etherates act as sources of GeHalz,
i. e. germanium analogues of dihalogenocarbenes [I]. The
reaction diagram shows the reactions of (2) with acetylene,
ethylene, and butadiene (ca. 20 'C, normal pressure). The
other etherates ( 3 ) react analogously. Compounds (4) and
(6) react with CH3MgBr to yield the hexamethyl derivatives,
and (8) gives rise to the dimethyl derivative. Yields: ( 4 )
50-607;; (5) 20-30%; (6) 50-60%; (7) 20-25%; (8)
60-65 %; (9) ca. 30 "4.
Both RMgHal and RLi cause (2),
(3), GeIz, other etherates of ( I ) , and also the complex compound formed from ( I ) and pyridine to undergo telomerization of the GeCIz or of the GeR2 formed from it - a property
characteristic of carbenes and their analogues ; R-[GeRz],-R
(n usually 2 2) and small quantities of cyclopolymers
[-CeR2-ln with n = 4 or 6 are formed.
Like HGeC13 and the stable compounds GeHalz and SnHal2
[2], the etherates of HGeHal3 are strong reducing agents,
being oxidized to GeHal4 or SnHal4. For example, ( 1 ) and
p r i
ClzXGe - C H- CH - G e C 13 (4)
( - C H z - C H z - C e C l z - 1,
Structure and Properties of
Trihalogenogermane Etherates
By Dr. 0. M. Nefedov, cand. chem. S. P. Kolesnikov, and
Dipl.-Chem. V. I. Sheichenko
N. D. Zelinskij Institute for Organic Chemistry, Academy of
Sciences of the U.S.S.R., Moscow (U.S.S.R.)
HGeC13 (I) associates with diethyl ether to forme an etherat
2(CzH&O.HGeC13 (2), a bright yellow oil which is insoluble
in excess diethjl ether, but which dissolves ( I ) . The infrared
spectrum of (2) does not contain a Ge-H band, which
would be expected to occur between 2000 and 2200 cm-1.
The N M R spectrum of (2) [60 Mc, tetramethylsilane as
internal standard] shows only the signals of the CH2 and
CH3 groups of the ether (8 = -1 to -4 pprn) plus a singlet
at 8 = -14.7 to -14.5 ppm. Comparison of this figure with
the values for HGeCI3 (-7.6 ppm) and dilute hydrochloric
acid (-16.6 ppm) shows that the H-Ge bond in HGleCs is
strongly polarized, hence the proton attaches itself t o the
lone electron pairs of the ether's oxygen atoms.
C1,XGe - CH2- CHyGeC13 161
[ -CH=CH-GeCl,-
(2) reduce ArN3 to ArNZNHz, and ArN02 to ArNH2.
Cautious evaporation of the etherate (2) leaves a residue of
GeClz (probably polymeric [GeCIz],,) in 50-60 % yield as
a n amorphous or finely crystalline bright yellow to red
powder. This is soluble in acetone but insoluble in diethyl
ether and hydrocarbons, and decomposes at 140 "C. Atmospheric moisture hydrolyses it to GeO; it reacts with benzyl
chloride to form H&-CHz-GeC13.
The structure (10) proposed for the etherate (2) explains the
ease of formation of GeC12 by the dissociation:
+ GeCI2 +
and also its greater reactivity, compared with that of the
stable compounds GeIz and SnHal2 [3].
HCC13 scarcely reacts with diethyl ether ( L ~ C - H = 0.5
ppm), and HSiC13 not at all ( A s s i - ~ = 0 pprn). The
difference in behavior of HGeC13 and HSiC13 can probably
Angew. Chem. ititernat. Edit. 1 Vol. 3 (1964)
No. 7
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salt, benz, biogenetic, cyclization, quinolizinium, possible, typed, acetoacetaldehyde, hydrobromide, dihydroxyphenethylamine
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