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New Possibilities of Direct Substitution of Adamantane.

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Table I . Yields of ATP (calc. on the 84 % ADP used on simultaneous
oxidation of equivalent amounts of (TBA)zHPO,,, (TBA)3ADP, and
TBA niercaptoacetate by 1.2, 2.0, and 5 . 0 equivalents of bromine.
1_ _1
1.2
Br2 (equiv)
I
2.0
1
I
5.0
1: 1
~ _ _ ~ _ _ _ _
without
out
Yield (%)
of ATP
0
____-
-
~
____Net yield (%)
of ATP
Although 1-adamantanecarbaldehydes lose CO o n heating
under nitrogen, they are converted i n t o stable dimethyl
acetals when dissolved in methanol containing hydrogen
chloride.
3,5,7-Trimethyl-I-adumantunecarbaldehyde:
1 -?err- Butyl-2-(3,5,7-trimethy~-l-adamantyl)aziridinone~~~
(1.50g) is heated to 100°C under nitrogen for a period of
15 min with a mixture of water (75 ml) and methane-sulfonic
acid (7.0 9). The aldehyde formed is steam-distilled into an
ice-cooled receiver, filtered off, and dried over PzO5 in a
vacuum; yield 1.03 g (96%); m.p. 74-75 "C.
5.8
Received: August 27, 1968; revised: September 19, 1968 [ Z 878 IEI
German version: Angew. Chem. 80, 970 (1968)
I
Received: September 18, 1968
[Z 876 1El
German version: Angew. Chem. 80, 915 (1968)
-~___
[*I Prof. Dr. Th. Wieland and Dr. E. Bauerlein
Institut fur Organische Chemie der Universitat
6 Frankfurt/Main, Robert-Mayer-Strasse 7-9 (Germany)
Present address: Institut fur Chemie im
Max-Planck-Institut fur medizinische Forschung
69 Heidelberg, Jahnstrasse 29 (Germany)
[l ] Model Experiments o n Oxidative Phosphorylation, Part. 10.Part 9: [4].
[2] Th. Wieland and E. Bauerlein, Mh. Chem. 98, 1381 (1967).
[3] Th. Wieland and E. Bauerlein, Chem. Ber. 100, 3869 (1967).
141 Th. Wieland and H . Aquila, Chem. Ber. 101, 3031 (1968).
[ 5 ] Th. Wieland and H . Aquila, Angew. Chem. 80, 190 (1968);
Angew. Chem. internat. Edit. 7, 213 (1968).
[6] E. Buuerlein and Th. Wieland, Chem. Ber., in press
[*I Dr. K. Bott
Forschungslaboratorien der Chemische Werke Huls A.G.
437 Marl (Germany)
111 V . L. Narayanan, US-Pat. 3300480 (1967),Squibb and Sons.
[2] K. Bott, Tetrahedron Letters 1968, 3323.
[3] H . Stetfer and E. Rauscher, Chern. Ber. 93, 1161 (1960).
[4] K . Boft, Angew. Chem. 79, 943 (1967); Angew. Chem. internat. Edit. 6 , 946 (1967).
[ S ] D. E. Applequist and L. Kaplan, J. Amer. chem. SOC.87,2194
(1965)
New Possibilities of Direct Substitution of
Adamantane
By H. S f e f t e r ,M. Krause, and W.-D. Last[*]
An ionic mechanism has been proposed for halogenation of
Synthesis of 1-Adamantanecarbaldehydes
By K . Bo?t[*l
According to a process described in the patent literature [ I ]
free I-adamantanecarbaldehydes can be prepared by reduction of 1-[1-(adamantanecarbonyl)]aziridinesusing LiAIH4.
We have now found that I-adamantanecarbaldehydes (4)
can be obtained in essentially higher yields (92-96%) by decomposition of the aziridinones ( I ) with aqueous mineral
acids (Table 1). Compounds (2) and ( 3 ) are assumed t o be
intermediates because the aldimonium salts (3) can be isolated quantitatively on working in anhydrous ether [21.
adamantane "1; correspondingly. Friedel-Crafts catalysts
catalyze this reaction. Adamantane can be halogenated also
by halogenated hydrocarbons in the presence of such catalysts [21. Thus treating adamantane with aluminum chloride
in carbon tetrachloride at room temperature gives a mixture
of 1-chloroadamantane ( I ) [ I ] and 1,3-dichloroadarnantane
(2) [31 in 84 % yield.
,-
q1
c1
I "
13) 7 2 %
Table I .
Characterization of the aldehydes ( 4 )
Aldehyde [a]
Dimethyl
acetal
Aldehyde
Oxime
Aldehyde
Dimethyl
acetal
I-Adamantyl
I-Adamantyl
139-141 [bl
40-41
3-Methyl-I-adamantyl
Colorless
oil
76-11
74-75
3-Methyl- 1 -adamantyl
3,5,7-TrimethyiI-adamantyl
3,5,7-TrimethyI1-adamantyl
1722 [cl
1710
1710 [cl
54-55
[a] First characterized as 2,4-dinitrophenylhydrazone[31.
[ b ] Described in ref. [ I ] as an oil; according to ref. [Sl, m. p. 195 to
197.3OC.
[cl KBr disc.
894
Using thionyl chloride instead of halogenated hydrocarbons
also affords chlorinated adamantanes. However, surprisingly,
at -15 "C I-adamantanesulfinyl chloride (3) is formed in
72% yield. On increase in the temperature the proportion of
( 3 ) formed decreases, and 1,3,5-trichloroadamantane[31 is
the main product at the boiling point. I-Chloroadamantane
( I ) always gives a smaller proportion of the sulfinyl chloride
(3) under comparable conditions. We assume that a chain
reaction occurs in which the I-adamantylium ion R Q
participates.
RQ
+
SOClz
C l @ + RH
+ RSOCl + CIS
+ R @ + HCl
The chloride ( 3 ) can be converted into methyl l-adamantanesulfinate ( 4 ) (colorless crystals, m.p. 44-46 "C) i n 83 % yield
by means of boiling anhydrous methanol (6 h). and this ester
is converted into I-adamantanethiol ( 5 ) [41 in 90% yield by
LiAIH4 in anhydrous ether (17 h, 36'C). Further, the acid
Angew. Chem. internat. Edit,
Vol. 7 (1968)
NO. I 1
chloride ( 3 ) is converted by 50,;; sodium hydroxide at room
temperature into 1-adamantanesulfinic acid ( 6 ) (yield 61 Y,;
m.p. 132-134°C in a sealed tube), which is oxidized almost
quantitatively by hydrogen peroxide t o 1-adamantanesulfonic acid (7) 151. The chloride ( 3 ) can also be used for preparation of esters and amides of I-adamantaneulfonic acid
that were not previously accessible. For this purpose ( 3 ) is
treated with alcohols or amines, yielding l-adamantanesulfinic acid derivatives, which can be oxidized in good yield by
potassium permanganate in boiling acetone. For instance,
oxidation of ( 4 ) gives methyl 1-adamantanesulfonate ( 8 )
(colorless crystals, m.p. 113-114 "C) in 8 5 % yield. 1-Adarnantanesulfonamide (10) (colorless needles, m.p. 197 to
198OC) is obtained analogously in 9 5 % yield, the l-adamantanesulfinamide (9) (m.p. 141-142 "C) being prepared
in 75 '%, yield by treating ( 3 ) with concentrated aqueous ammonia for 2 h at 100°C.
R
--
however, can only be proved by X-ray structural analysis.
Recently, microcrystalline spherulites of tRNA,F. ro,i
Meth
tRNA;ZLst have been obtained [31; however, single crystals
are essential for an X-ray structural analysis. In this communication we wish t o report o n the cryFtallizztion of a
t R N A from brewers' yeast.
tRNS;::st
was isolated from a commercially available
(Boehringer, Mannheim) soluble yeast-RNA. The workingup involved a partition step, as described by Khym14J and
subsequent chromatography on benzoylated DEAE-cellu(82% aminoacylatable) thus oblose[5J31. The tRNA:&,
tained was first dialyzed against 10-2 M EDTA and then
against 10-3 M Mg 2+ and 10-2 M K'.
The non-bonded metal ions were subsequently removed by
dialysis against distilled water. Dioxane, from a solution of
dioxane,'water (35:lOO v h ) was distilled via the vapor phase
into a 1.5 "/, solution of t R N A in dioxandwater (20:lOO v!v)
at room temperature in a dessicator. Crystals of rhombohedral form (Fig. 1) were formed along the vessel wall at the
surface. The crystals were about 0.15 mm in length, about
0.07 mm wide, and were considered t o be of a thickness of
0.01-0.02 mm.
I n polarized light extinction was observed at each 90" interval, thus suggesting an orthorhombic system. On excitation
by light of 325 nm wavelength the crystals exhibited strong
blue fluorescence, as does the tRNAT,h,e,, itself. After redissolution of the crystals, the tRNA;&,
was aminoacylatable t o the same extent as the starting material.
1-adamantyl
I-Adfli,iantanesuljnyl chloride:
AICI, (40 g) and SOClp (200 ml) are treated with adamantane
(40.8 g) with exclusion of moisture at -15 "C over a period of
2 h; the mixture is then stirred for another 1 h at the same
temperature. The clear solution is allowed to warm to room
temperature, the excess of SOClz is removed under vacuum,
and the residue is taken up in CC14 (300 ml) and cautiously
treated with water. The organic phase is separated off, dried
over CaC12, and the solvent is removed. The oily residue is
distilled at 130-136 "Ci3- 4 torr, the chloroadamantanes
occurring in the first runnings. Yield 4 7 g (72%, m.p. 4 2 to
44 "C).
Received: Sep!ember 19, 1968
[Z 879 IEI
German version: Angew. Chem. 80, 970 (1968)
Fig. 1 . Crystals of tRNAFt:st
[*] Prof. Dr. H. Stetter, Dr. M. Krause, and
Dip1.-Chem. W.-D. Last
Institut fur Organische Chemie der Technischen Hochschule
51 Aachen, Templergraben 55 (Germany)
[l] H . Stetter, M . Schwarz, and A . Hirschhurn, Angew. Chem.
71, 429 (1959); Chem. Ber. 92, 1629 (1959); H . Stetter and C .
Wul', Angew. Chem. 72,351 (1960); Chem. Ber. 93,1366 (1960);
R . C . Fort and P. v. R . Schleyer, Chem. Reviews 64, 277 (1964).
121 M. Kiause, Dissertation, Technische Hochschule Aachen,
1967.
[3] H. Stetter and C. Wul'; German Pat. 1101 410 (Feb. 29,
1960), Farbenfabriken Bayer; Chem. Abstr. 56, P 14120a (1962).
[4] H . G. Thomas, Dissertation, Technische Hochschule Aachen,
1965.
[5] G. W. Smith and H . D . Williams, J. org. Chemistry 26, 2201
(1961).
Single Crystals of Phenylalanine-Specific Transfer
Ribonucleic Acid
By F. Cramer, F. v. d. Haar, W. Saenger, and E. Schlimme[*I
On the basis of the base-pairing rules and the results of chemical and biochemical experiments, suggestions have been
made concerning the secondary 111 and tertiary 121 structures
of transfer ribonucleic acid (tRNA), the validity of which,
Angew. Chem. internal. Edit.
1 Vol. 7 (1968)1 No. I 1
yeast in polarized light.
The crystals were kept in the upper part of the Debye-Schemer type
crystallization tube (4mm diameter) for the photographic recording.
The crystals situated at the places marked by arrows are oriented such
that they do not rotate the plane of the polarized light. (Magnification
approx 1 3 3 X . ) [**I
Received: October 23, 1968
[Z 889 lE]
German version: Angew. Chern. 80, 969 (1968)
[ * ] Prof. Dr. F. Cramer, Dr. F. v. d. Haar, Dr. W. Saenger,
and Dr. E. Schlimme
Max-Planck-Institut fur experimentelle Medizin,
Abteilung Chemie
34 Gottingen, Hermann-Rein-Strasse 3 (Germany)
[l] R . W. Holley, J . Apgar, G . A . Everett, J . T. Madison, M. Marquisee, S. H . Merriil, J . R . Penswick, and A. Zamir, Science
(Washington) 147, 1462 (1965).
[2] F. Cramer; Angew. Chem. 79, 653 (1967); Angew. Chem.
internat. Edit. 6,642 (1967); F. Cramer, H. Duepner, F. v. d. Haar,
E. Schlimme, and H . Seidel, Proc. nat. Acad. Sci. USA, in press;
W. Fuller and A. Hudgsun, Nature (London) 215, 817 (1967).
[3] B. F. C. Clark, B. P. Doctor, K. C. Holmes, A. Klug, K . A .
Marcker, S. J. Morris, and H . H . Paradies, Nature (London) 219,
1222 (1968); H. H. Paradies, FEBS Letters, in press.
[4] J. X . Khym, Biochemistry 2, 401 (1963); J. biol. Chemistry
240, PC 1488 (1965).
[S] I. Giilam, S. Millward, D . Blew, M. v. Tigerstrum, E. Wimmer,
and G. M . Tener, Biochemistry 6, 3043 (1967).
[6] F. v. d. Haar, unpublished.
[**I We thank Dr. V . Neuhuff for the photomicrographs.
895
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