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Optically Active Trisbiphenylenephosphates.

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I
Cycloalkyl ester
Cyclopentyl acetate
Cyclohexyl f o r m a t e
Cyclohexyl a c e t a t e
Cyclohexyl valerate
Cycloheptyl acetate
Cyclododecyl fo rm a t e
Cyclohexyl f o r m a t e [bl
Cyclohexyl f o r m a t e [c]
1
400
400
400
: "4
420
400
410
I
1
76.1
99.7
62.6
97.2
cyclopentanone (65.5)
cyclohexanone (77.4)
i cyclohexanone (50.3)
cyclohexanone (42.9)
cycloheptanone (49.2)
cyclododecanone (71.6)
cyclohexanone (trace)
Cycloalkene
(yield 1041)
cyclohexene (20.8)
cyclohexene (50.7)
cycloheptene (33)
cyclododecene ([a])
cyclohexene (97.3)
cyclohexene ( 2 . 5 )
Optically Active Trisbiphenylenephosphates
By Dr. D. Hellwinkel
charged was around 97.8 mole- %. About 0.36 mole- cyclohexene was formed as a by-product. The residual content
of cyclohexyl esters (calculated as acetate) was only 0.3 %.
Received: Feb ru ary ls t, 1965;
s u p p lem en ted : Feb ru ary ISth, 1965
[Z 918/745 I E ]
G e r m a n version: A n j e w . C h e m . 77, 346 (1965)
[*] In collaboration with G . Forberger, S. Janncek, and
F. Langohr.
Synthesis of Cyclotri-L-prolyl, a Cyclotripeptide
Having a Nine-Membered Ring [I]
By Priv.-Doz. Dr. M. Rothe and Dip1.-Chem. K.-D. Steffen,
in collaboration with Dr. Ilse Rothe
Organisch-Chemisches Institut
der Universitat Mainz (Germany)
N o synthesis of cyclotripeptides has hitherto been achieved
because linear tripeptides normally undergo dimerization
during ring closure t o give cyclohexapeptides with an
unstrained 18-membered ring.
On cyclization of tri-r-proline [hemihydrate, 111.p. 125 to
130 "C (decomp.)] using either the p-nitrophenyi ester or the
phosphite method [2] and simultaneously applying the
dilution principle, we obtained an 88 %, yield of readily
crystallizable, sublimable cyclotri-i-prolyl in thin-layer
chromatographic and analytical purity [m.p. 338 "C (decamp.), [a]$' = +48.5 (c = 0.48 in methanol)]. The size of
the ring is indicated by the partial hydrolysis of the compound with 0.1 N Ba(OH)2 [5 min at 100 "C] to give proline,
diproline, and triproline, and by the results of molecularweight estimations (calc. 291 ; found by the method of Rast
in 1,4-cyclohexanecarbolactam:293 ; by mass spectrometry:
291 131).
L-Prolyl-r-prolylglycinc,on the other hand, yields only the
cyclohexapeptide [trihydrate, m.p. 242 "C (decomp.);
[a]L5 = -140.0' (c = 0.57 in water)] in 21 "/: yield by both
ring closure methods. Here the infrared spectrum contains
an amide II band at 1550 cm-1, indicating trons-amide
configuration of the 18-membered ring. Partial hydrolysis
here gives rise t o linear hexapeptides of molecular weight 502
(determined by mass spectrometry; calc. : 502).
lnstitut fur Orgdnische Chemie
der Universitat Heidelberg (Germany)
The formal resemblance between the trisbiphenylenephosphate anion [ I ] and the chelate complexes of hexacoordinated
transition metals [2] made it appear likely that this ate-complex ( I ) of pentavalent phosphorus would have an octahedral
structure and should therefore be separable into optically
active antipodes.
Treatment of lithium trisbiphenylenephosphate with a n equivalent amount of N-methylbrucinium iodide in methanol
results in quantitative precipitation of a mixture of the two
diastereoisomeric N-methylbrucinium trisbiphenylenephosphates. Several recrystallizations from acetone led to a 25 X
yield of pure (-)-methylbrucinium (-)-trisbiphenylenephosphate, m.p. 234-236'C, [a]:;: = 1250+ 15 (c = 0.8-1.0
in CH2C12). After removal of all crystalline fractions from the
mother liquors, (-)-methylbrucinium (+)-trisbiphenylenephosphate, which does not crystallize out, can be precipitated with methanol; m.p. 230-234OC. Here the highest rotations measured were [a]:;; = 950+ 50" (c = 0.8-1.0 in
CH2C12).
The diastereoisomeric salts react smoothly with potassium
iodide in acetone to give N-methylbrucinium iodide and colorless potassium trisbiphenylenephosphates ( I ) , which have
the remarkably high specific rotations [a]$$; = i1930 2: 20"
= T 10150 i 100"; m.p.
(c = 0.4-0.7 in acetone); [MI$;
295-298 "C (decomp.).
When the optically active potassium or sodium salts ( 1 )
were treated with bisbiphenylenephosphonium iodide 11] in
methanol, the two stereoisomeric yellow phosphonium phosphate complexes (Z), [a]:$: = r 1265 i 15 (c = 0.7-1.0 in
= <: 10 410 fi 120", m.p. 247to
dimethylformamide), [MI$:
250 'C (decomp.), were obtained.
Received. Feb ru ary 11th. 1965
IZ 9161740 IE]
G e r m a n version Angew. C h e m . 77, 347 (1965)
(2)
[ I ] Cyclic Peptides, Part XI. - Part X : M . Rothe et al., Angew.
Chem. 75, 1206 (1963); Angew. Chern. internat. Edit. 3, 64
Received: February 12th, 1965
[ Z 9171750 IEI
G er man version: Angew. Chem. 77, 378 (1965)
(1964).
121 M .
Rothe et a\., Angew. Chem. 7 1 , 700 (1959).
[3] Determined by Dr. Reliqg, FrankfurtiMain-Hoechst (Cer-
[I] D. Hellwinkel, Chern. Ber. 98, 576 (1965).
[2] F. P. Dwyer and D. P . Mellor: Chelating Agents and Metal
many).
Chelates. Academic Press, New York 1964.
356
Aiigew. Cheni. imernd. Edit.
Vol. 4 (1965) 1 No. 4
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