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Formation of Adenosine Triphosphate (ATP) from Adenosine Diphosphate (ADP) and Phosphate During Oxidation of Durohydroquinone Monoacetate.

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also occurs, so that 50% of the G e used or 8 0 % of the Sn
used is recovered as metal. Calculated o n the proportion of
reaction that leads to linkage, the yields are 70% for (3c)
and 50-60% for (3d). Like (3a) and (361, the compounds
(3c) and (3d), which are spherical top molecules, colorless,
crystallizing well from CH3CN, and subliming at 60 "C/lO-4
torr. have unusually high melting points and volatility.
They are decomposed by K O H to (GeH2), and Sn, respectively. Alcohol and H20 attack them more slowly than in the
case of (36).
I I
313-321
[3]
:::-236
similarly during the action of oxidizing agents on S-acyl
compounds such as thiolactones ( 2 ) [2,51.
The use of hydroquinone for oxidative formation of activated
acyl groups also makes it possible to obtain ATP from A D P
and phosphate. In our reaction system the energy-rich acetyl
group produced by oxidizing durohydroquinone monoacetate ( 3 ) with bromine or tetrabromo-o-benzoquinone
reacts with phosphate (or ADP) to give acetyl phosphate (or
acetyl-ADP), which reacts with ADP (or phosphate) to give
ATP.
119.5
6.3
0.21
0.24
120.0
120.5
6.5
6.7
0.29
120.7
6.7
[b] 25% Solution in CCII, TMS and cyclohexane as internal standards, Varian A 60.
[ c ] Limit of resolution power
The 1H-NMR spectra show a steady progression of all 8and J-values and no irregularities as for compounds ( I ) and
(2). The vibrations of the Si4E(1v) skeleton obey the selection rules for ideal tetrahedrons. The fundamentals v1 to v4
are at the following frequencies (in cm-1 & 2 cm-1):
s-co
O X + [ I
(3a)
(36)
(3ci
(3d)
YI =
382
328
319
31 1
Vz =
151
y3:
90
68
58
673
457
361
330
-
0
ox-s-co
I
I
v 4 = 176
101
a9
73
The positions of the stretching vibrations confirm qualitatively that, in spite of the lower polarity, the (sp3)Si-(sp3)Sn
a-bond in (3d) (v = 326 cm-1) is stronger than the
(sp-')Si-(sp3)Sb bond in [(CH3),Si]3Sb (v = 319 cm-9,
whereas the Si-C bond in (3a) is appreciably weaker than
the Si-N bond in [(CH3)3Si]3N because the former has less
s-character and less polarity and no n-contribution to strengthen it. We shall report the force constants o f (3a)-(3d)
together with the complete analysis of the vibration spectra
i n a future communication.
Received: December 19, I967
[Z685 IE]
German version: Angew. Chem. 80, 192 (1968)
[*] Doz. Dr. H. Burger and Dip1.-Chem. U. Goetze
Institut fur Anorganische Chemie
der Technischen Hochschule
33 Braunschweig, Pockelsstr. 4 (Germany)
[l] H . Eiirger, Fortschr. chem. Forsch. 9, 1 (1967); H. Eiirger,
U.Goetze, and W. Sawodny, Spectrochim. Acta, in press.
121 R. L. Merker and M . J. Scott, J. organometallic Chem. 4, 98
(1965).
[3] H. Gilman and C. L . Smith, J. Amer. chem. SOC.86, 1454
(1964), J. organometallic Chem. 8, 245 (1967).
Formation of Adenosine Triphosphate (ATP) from
Adenosine Diphosphate (ADP) and Phosphate
during Oxidation of Durohydroquinone
Monoacetate11 1
B y Tlt. Wieland and H. Aquiia [*I
We have demonstrated the conversion of oxidation energy into a high group-transfer potential [21 for the case of formation
of an energy-rich phosphoryl linkage, H203P-X, duringoxidation of S-phosphoryl thiols [31 or hydroquinone monophosphoric esters (1) 141. Energy-rich acyl groups (which can
transfer their acyl group to phosphoric acid) are formed
Angew. Chem. internat. Edit. / VoI. 7 (1968) / NO.3
(3)
H,PO,
+ ADP
(H~O~P-O-COCHS)
__f
ATP
Formation of acetic anhydride on oxidation of 2-methyl-l,4naphthohydroquinone-1-acetate by N-bromosuccinimide in
glacial acetic acid has recently been described by Thanassi and
Cohen [61.
We obtained durohydroquinone monoacetate ( 3 ) in ca.
35 % yield by acetylation of durohydroquinone at 0 O C with
acetyl chloride in pyridine, together with the diacetate from
which it was separated by utilizing its slower rate of migration
o n chromatography on silica gel with chloroform as eluant.
Recrystallization from ethanoliwater and then from benzene
gave material melting a t 146.5-147.5 "C.
For oxidative phosphorylation 48 mg (0.1 mmole) of
ADP.3H20 (C.F. Boehringer und Soehne, MannheimWaldhof), 0.87 ml of a 0.115 M solution of 85 % phosphoric
acid in dioxane, and 5 ml of a 0.1 M solution of tetrabutylammonium hydroxide in propan-2-01 (Merck, Darmstadt)
were placed in a 50-ml flask and evaporated on a rotary
apparatus in a vacuum. The residue was moistened with ethanol and the latter was then removed. After this procedure
had been repeated several times, the residue was dried for 5 h
at oil-pump vacuum over P2Os and solid KOH in a desiccator; it was then dissolved in 5 ml of pyridine (dried over
CaH2) and, after addition of 20.8 mg of durohydroquinone
monoacetate, treated with 0.014 ml (0.25 mmole) of bromine
or 47 mg (0.11 mmole) of tetrabromo-o-benzoquinone with
ice cooling and magnetic stirring. The mixture was stirred in
the ice-bath for half a n hour and for a further 1.5 h a t 20 "C
then evaporated in a vacuum. The residue dissolved wholly
in 2.0 ml of methanol. 0.5 ml of this solution was placed on
a 20 cm x 20 cm thin-layer plate (0.5 mm of silica gel HF254,
Merck), and the chromatogram was developed first with
chloroform/methanol (10:3), then dried with a fan, and fur-
213
ther developed with propan-1-ol/conc. ammoniaiwater
( 6 :3: 1). After drying, the lower fluorescence-quenching ATP
zone was removed and the silica gel was eluted with 25 ml of
0.05 M Tris buffer (PH = 7.55). The yields of ATP determined
enzymically [71 and referred t o the A D P used were: o n oxidation with bromine 6.0 and 6.8%; on oxidation with tetrabromo-o-benzoquinone 9.5 %; without oxidizing agent 0.0 %;
and without acetyldurohydroquinone monoacetate 0.0%.
Received: December 18, 1965
[Z 686 IE]
German version: Angew. Chem. 80, 190 (1968)
[*I Prof. Dr. Th. Wieland and Dip1.-Chem. H. Aquila
Institut fur Organische Chemie der Universitat
6 FrankfurtiM., Robert-Mayer-Str. 7-9 (Germany)
[I] Part 8 of Model Experiments on Oxidative Phosphorylation.
- Part 7: IS].
121 Th. Wieland and E. Bauerlein, Naturwissenschaften 54, 80
(1967).
[3] Th. Wieland and R. Lnmbert, Chem. Ber. 89, 2476 (1956).
[4] Th. Wielandand F. Pattermann, Angew. Chem. 70,313(1958);
Chem. Ber. 92, 2917 (1959).
[5] Th. Wieland and E. Bauerlein, Chem. Ber. 100, 3869 (1967).
[6] J. W. ThanassiandL. A . Cohen, J. Amer. chem. SOC.89, 5733
(1967).
[7] H . (1. Bergmeyer: Methoden der enzymatischen Analyse.
Verlag Chemie, Weinheim 1962.
Syntheses by Means of 1-Alkylidene- and
l-(Arylalkylidene)-3-pyrazolidone N,N-Betaines,
a New Type of Stable Azomethine Imine
By H . Dorn and A . Otto
Azomethine imines have, it is true, been postulated as intermediates in the formation of hexahydro-1,2,4,5-tetrazines
from 1,2-disubstituted hydrazines and aldehydes [I], but they
RZ
M.p.
-
( "C)
CH3
CHI
Cyclohexylidene
H
C6Hs
H
P-CI-C~H~
H
p-HjCO-C&
H
H
H
H
H
156-160
155-160
205-208
214-217
187- 189
H
2-Fury1
H
213-7.16
H
5-Nitro-2-fury1
H
H
C6Hs
CHI
Decomp.
from 230
139- 141
I
H
H
80-81
90-91
H
H
H
H
86-87
105-106
57-58
59-60.5
CH3
[a1 In KBr;
214
72-72.5
have been isolated in only two cases, namely, as deep blue
"anhydro bases" from N-(ary1amino)pyridinium iodides [21
and as orange-red products from arenediazo cyanides and
diazofluorene [31. We have found that stable azomethine
imines are obtained very simply from 3-pyrazolidone and
carbonyl compounds in S0-90% yield. This reaction is
generally applicable; it takes place exothermally and either
without a solvent or in methanol. The crystaIline azomethine
imines ( 2 ) are dried in a vacuum over P4O10 and then recrystallized from alcohols or dioxane. They are colorless unless
substituents R1 are introduced that deepen color (NO2, 4-dialkylamino).
Because of their molecular weights and their chemical behavior the products ( I ) cannot be either hexahydro-l,2,4,5tetrazines or p-lactams. Their acid-catalyzed hydrolysis
regenerates the starting materials quantitatively. Catalytic
hydrogenation (methanol, Adams Pt, atmospheric pressure)
leads t o quantitative yields of 1-substituted 3-pyrazolidones
(3). Since 3-pyrazolidone 141 and its C-alkyl derivatives [ 5 ]
have recently become readily accessible, this reaction offers
a very simple synthesis of 1-substituted 3-pyrazolidones [61.
The position of C R R l in ( I ) and (3) follows from synthesis
of (3a) and (3b) by way of the 3-amino-N-nitrosopropionic
ester (4)and of (3c) by acid hydrolysis of 1-benzyl-3-iminopyrazolidine (2c) which is obtained by cyclization of 1-
benzyl-l-(2-~yanoethyl)hydrazine
"1.
In agreement with the azomethine imine structure, the I R
spectra of ( I ) contain intense bands at 1670 and 1600 cm-1,
of which the latter, more intense, band is to be assigned to
the carbonyl vibration. Their shift to lower frequencies
compared with the bands of the corresponding pyrazolidones
indicates participation of the limiting structure (1'). The
N M R spectra of ( l a ) , (Ic), and (lei, and of compounds
analogous to ( I b ) that are synthesized from 2,2,6,6-tetradeuteriocyclohexanone correspond t o the azomethine imine
structure ( I ) ; ( l a ) (in CDC13) shows two singlets at T = 7.62
and 7.73 for the two methyl groups.
v (CO)
(cm-1)
v (C=N)
1600 [a1
1605 [ a ]
1600 [a]
1600 [a]
1610 [bl
1613 [a]
1608 [bl
1604 [a]
1600 [a]
1665 [a]
1660 [a]
1680/1655 [a]
1675/1660 [a]
1687/1667 [b]
1680/1662 [a]
1680/1655 [b]
1678/1658 [a]
1680/1660 [a1
1596 [a]
1668 [a]
(cm-1)
1700 [bl
1700 [bl
1685 [a]
1705 Ibl
1695 [bl
1695 Ibl
1688 [bl
1696 [a]
1698 [bl
[b] In CHCI3.
Angew. Chem. internat. Edit.
Val. 7 (1968) 1 No. 3
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atp, oxidation, triphosphate, diphosphate, phosphate, adenosine, formation, adp, monoacetals, durohydroquinone
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