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Hydrogen Fluoride-Potassium Hydrogen Phosphite (11) an Unusual Lattice Compound.

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three times with benzene (3 x 50 ml), and concentrated under
vacuum. On treatment of the residue with light petroleum
(b.p. S&7OoC), a crystalline precipitate of (4b) (9.4 g) appeared. Concentration of the light petroleum solution afforded a further crop of crystals (2.8 g) [m.p. 74-75 OC; I R
spectrum (KBr): 2170 cm-1 (vNC), 3380 cm-1 (vOH)]. A solution of (4b) ( 5 g) in dioxane (20 ml) was added dropwise (ice cooling) to a mixture of 2 N hydrochloric acid (50ml)
and dioxane (SO ml). After two hours’ stirring, work-up a t
room temperature yielded l-formylamino-2-phenyl-2-propanol (3.3 g).
Received: April 9, 1970
[ Z 197 IE]
German version: Angew. Chem. 82, 482 (1970)
[*] Dr. A. Niirrenbach and Dr. W. A. Boll
Badische Anilin- und Soda-Fabrik AG
67 Ludwigshafen (Germany)
Prof. Dr. U. Schollkopf and Dr. F. Gerhart
Organisch-Chemisches Institut der Universitat
34 Gottingen, Windausweg 2 (Germany)
[ l ] Syntheses with a-Metalated Isocyanides. Part 6. - Part 5:
D . Hoppe and U . Schollkopf, Angew. Chem. 82, 290 (1970);
Angew. Chem. internat. Edit. 9, 300 (1970).
[2] U.Schollkopf and F. Gerhart, Angew. Chem. 80,842 (1968);
Angew. Chem. internat. Edit. 7, 805 (1968).
[3] D. S. Mafteson and R . A . Bailey, J . Amer. chern. SOC.YO,
3761 (1968).
141 In this connection, see also F . Gerharf and U. Schollkopf,
Tetrahedron Letters 1968, 6231; Th. Kauffmann, E. Koppelmann, and H . Berg, Angew. Chem. 82, 138 (1970); Angew.
Chem. internat. Edit. 9, 163 (1970).
[ S ] On addition of ethanol, methanol, or water, Az-oxazolines
are obtained, which are also formed on treatment of ( 4 ) with
alkali.
Ar-CHy
(C)
C~HS
p-CHa-Cdb
P-CH3OC6H4
(4
CsHs
lbi
H
H
H
CH,
3
2
12
30
Organisch-Chernisches Institut der Universitat
34 Gottingen, Windausweg (Germany)
[l] Syntheses with or-Metalated Isocyanides, Part 7. - Part 6:
W. A. Boll, F. Gerhart, A . Niirrenbach, and U. Schollkopf,
Angew. Chem. 82, 482 (1970); Angew. Chem. internat. Edit. Y,
458 (1970).
[ 2 ] D . Hoppe and U . Schollkopf, Angew. Chem. 82, 290 (1970);
Angew. Chem. internat. Edit. 9, 300 (1970).
[3] The 2-oxazoline must be free from cyanide ions and isocyanide since these poison the catalyst.
Hydrogen Fluoride-Potassium Hydrogen
Phosphite (1/1), an Unusual Lattice Compound[**l
By Hans Falius, Dietrich Mootz, and Horst Altenburg[*l
KF
NHCHO
I
-COzC,H5
R1
7
I
(a)
[*] Prof. Dr. U. Schollkopf and Dip1.-Chem. D. Hoppe
~
Phenylalanine and its derivatives (e.g. tyrosine, thyroxine,
dopa, methyl-dopa, etc.) have attracted a great deal of
attention because of their biological activity. We have found
that N-formylphenylalanine ethyl esters (2), R1 = H, and
the a-methyl compounds (2),R* = CH3, can be prepared by
hydrogenolysis of 5-aryl-2-oxazoline-4-carboxylates( I ) [21
with e . g . palladium/activated charcoal in ethanol. Compounds (2) can be converted into phenylalanines by heating
with 20 % hydrochloric acid, while brief heating with potassium hydroxide in ethanol affords N-formylphenylalanines.
Hz
Received: March 13, 1970
[ Z 178 IE]
German version: Angew. Chem. 82,483 (1970)
Publication delayed at authors’ request
H F + KH[PHO3I
By Ulrich Schollkopf and Dieter Hoppel*]
-
A solution of ethyl 5-phenyl-2-oxazoline-4-carboxylate
12,31
(5.0 g, 23 mmoles) in dry ethanol (SO ml) is shaken a t room
temperature with 0.25 g of palladium/activated charcoal
(10 % palladium, Merck) under hydrogen (normal pressure);
in 3 hours 510 ml (22 mmoles) of hydrogen is taken up.
After flushing with nitrogen, filtration, and evaporation of
solvent there remains 5 g (99 %) of (2a) [NMR spectrum
(CCl4): CH2. T = 7.0 (d, J = 7 Hz); CH, T = 5.2 (m). IR
spectrum (film): 3320 cm-1 (vNH); 1740 and 1680 cm-1
(VC0)l.
Studies on phosphorofluoridous acid have led to the discovery
of the adduct H F . KH[PH03] ( I ) , which is stable only in the
solid state. It may be readily prepared by the following two
methods:
N-Formylphenylalanine Ethyl Esters
by Hydrogenolysis of Ethyl
5-Aryl-2-oxazoline-4-carboxylates
111
04N
Ar f t C 0 2 C z H ,
H
R’
N- Forniylphenylalanine ethyl ester (2a)
99
9s
9s
99
Cleavage of the C-0 bond in ( I ) , R1 = CH3, (2OoC, atmospheric pressure, proceeds ten times slower than in ( I ) ,
R1 = H; furthermore, substitution in the nucleus, e.g. by
methoxy groups, lowers the rate of hydrogenolysis. In these
cases it is advisable to carry out the hydrogenation at higher
temperatures o r under pressure.
Angew. Chem. internat. Edit. f Vol. 9 (1970)f No. 6
H . KHLPHOJ
F
+ H ~ [ P H O ~ ] ~ (1)
( I ) is obtained as large colorless monoclinic crystals; dfo =
2.139 gcm-3, m.p. 9 6 ° C . Unit cell: a = 6.692, 6 = 11.040,
c = 7.841 A; p = 127.88 O ; space group P21/c with Z = 4.
In the absence of moisture the crystals are stable at room
temperature; when kept in glass vessels, however, local
attack of the glass surface occurs. In aqueous solution, which
shows a strong acid reaction, the compound exhibits only the
reactions of its constituent ions; it cannot be reisolated
from this solution. The N M R spectra (in methanol and in
water) show only one fluorine signal alongside the resonances
characteristic of phosphorous acid. The adduct is therefore
not a hydrate of potassium phosphorofluoridite K[PHOzF] .
HzO, as was previously assumed. Its IR spectrum closely
resembles that of KH[PH03].
The properties of “phosphorofluoridous hydrate” described
by Heinz and ROhner[11 suggest that it is also a n adduct of
composition H F . Hz[PHO3], for phosphorofluoridous acid
is stable and the vPF frequency (about 884 cm-1 in the acid)
was not observed in the spectrum of this “acid hydrate”.
Unlike phosphorofluoridous acid 121, compound ( I ) is immediately oxidized completely to phosphate by iodine in
hydrogen carbonate solution. On alkalimetric titration it is
neutralized by two equivalents of alkali in two stages. When
( I ) is heated in a vacuum it loses H 2 0 and HF, loss of
weight setting in a t 115 OC, to give a mixture containing a
little K[PHOzF] and much KZ[P2H2051.
Preparation :
1. Equimolar amounts of Hz[PH03] and K F are vigorously
ground together, the mixture first becoming sticky and then
liquid. The syrupy liquid is extracted with hot methanol,
filtered, and allowed to cool; yield 30 %.
459
2. A mixture of KH[PH03] and 40% H F (molar ratio
1 : 1.5) is evaporated to dryness over P4O10 and KOH in a
vacuum desiccator. After a few days, the crystalline mass (or
sometimes syrup) is extracted with methanol as above.
Method 1 is superior to the other. Elemental analysis (K, P, F)
confirmed the composition of ( I ) ; mol. wt. found by alkalimetric titration to be 139 (calc. 140).
The corresponding ammonium compound could not be
prepared by the above method; attempted preparation of the
sodium compound yielded only the known adduct NaH[pH031 . H2IPH031.
X-ray analysis:
Three dimensional intensity data were measured with C U K ~
radiation on a n automatic single crystal diffractometer 131
( 0 / 2 0 scan). Several sets of overlapping data had to be recorded for fresh crystals because ( I ) is sensitive to moisture
and reacts with glass, as mentioned above. Data reduction
resulted in 857 observed independent structure amplitudes
which were used for determination of the structure by the
usual technique andirefinement to_R =,5.6 %.
The Figure is a schematic representation of two equivalent
formula units (without the potassium ions) arranged about
a center of symmetry. The positions of the hydrogen atoms
and the lengths of the PO bonds (two P-0 bonds of 1.502
and 1.512 8, and one P-OH bond of 1.566 A; standard deviation ca. 0.004 A) provide conclusive proof of the formula
HF . KH[PH03J (ruling out KF . Hz[PH03]). Adjacent
H[PHO3]- ions are linked by equivalent hydrogen bonds
0-H . . . 0 t o form centrosymmetric dimers.
The short hydrogen bond F-H . . . 0 (F . . . O distance =
2.383 A), which to our knowledge has not previously been
reported, is the most interesting feature of the structure.
Received: October 29, 1969;revised: March 10, 1970 [Z I90 IEI
German version: Angew. Chem. 82,443 (1970)
[*I Priv.-Doz. Dr. H. Falius
Institut fur Anorganische Chemie
der Technischen Universitat
33 Braunschweig, Postfach (TU): 7050 (Germany)
Prof. Dr. D. Mootz and Dr. H. Altenburg
Abteilung fur Rontgenstrukturanalyse
Gesellschaft fur Molekularbiologische Forschung mbH
3301 Stockheim uber Braunschweig,
Mascheroder Weg 1 (Germany)
[**I This work was supported by the Fonds der Chemischen
Industrie and the State of Niedersachsen.
[l] D . Heinz and M . Rohner, Z . Chem. 9, 113 (1969).
[2] B. BIaser and K . H . Worms, Z . anorg. allg. Chem. 360, 117
(1968).
[3] AED designed by W. Hoppe of Siemens.
It may be assumed that the reactiveL41 double bond of (1)
initially adds the anhydride group, which would give the
intermediate (3) in the case of (2). I n this communication we
wish t o present a well-founded argument for the existence
of a n intermediate such as (3).
Reaction of maleic anhydride (5) with 2-isopropyl- ( I n ) and
S-methyl-2-isopropyl-2-oxazoline( I b ) , respectively, gave
crystalline addition products which were assigned the structures (6a) and (66).
(7 4
Their 1R spectra showed carbonyl absorption bands a t 1780
and 1660 cm-1 which are typical of strained y-lactones and
six-membered iactams, respectively. The formulas are further
supported by elemental analyses, molecular-weight determinations, and N M R spectra. The exceptional ease of hydrolysis of (6a) to (7a), which is converted into a,a-dimethylcarballylic acid and ethanolamine by vigorous hydrolysis, deserves
attention.
1I , 1 l-Dimethy2-2,10-dioxa-5-azatricyclo[6.2.1.0~
.5]undecane6,9-dione (6a)
A solution of 2-isopropyl-2-oxazoline ( l a ) (0.8 mole) in dry
1,2-dichloroethane (200 g) was added dropwise to a stirred
solution of maleic anhydride (5) (78.4 g, 0.8 mole) in dry 1,2dichloroethane with exclusion of atmospheric moisture. The
reaction mixture was boiled for 90 min and, after part of the
solvent had been distilled off, allowed to cool, whereupon
119 g of (6a) crystallized; a further crop of 9 g was obtained
on concentration of the mother liquor (total yield 77 %). On
washing with dry ethyl acetate, (6a) was obtained as colorless crystals (m.p. 178-191 "C, decomp.).
(661, m.p. 137-1 39 OC, was prepared analogously in 48 %
yield.
Received: April 8, 1970
[Z 193 IEI
German version: Angew. Chem. 82, 448 (1970)
[*] Dr. R. Nehring and Dr. W. Seeliger
Addition of Maleic Anhydride to
2-Isoprop yl-2-oxazolne
By Rudolf Nehring and Wolfgang Seeliger [*I
2-Oxazolines ( I ) add anhydrides and chlorides of monocarboxylic acids while undergoing ring scission to give 2-acyloxyethyland 2-chloroethyl-N,N-diacylamines
[21. Reaction
with cyclic anhydrides, such as those of phthalic and succinic
acid (2) [31, affords N-(2-acyloxyethyl)-phthalimide and -succinimide (4).
460
Forschungslaboratorien der Chemische Werke Hiils AG,
437 Marl (Germany)
[I] R . C. Eldei$eld: Heterocyclic Compounds. Wiley, New
York 1957, Vol. 5, p. 388.
[2] R . Nehring and W. Seeliger, Liebigs Ann. Chem. 709, 113
(1967).
[3] S. P . Rowland, US-Pat. 2547494 (1951) and US-Pat.
2547542 (1951), Rohm & Haas Co.
[4] W . Seeliger, E. Aufderhaar, W. Diepers, R . Feinauer,
R . Nehring, W. Thier, and H . HelImann, Angew. Chem. 78,913
(1966); Angew. Chem. internat. Edit. 5,875 (1966); R . Feinauer
and W. Seeliger, Liebigs Ann. Chem. 698, 174 (1966).
Angew. Chem. internat. Edit.
1 Vol. 9 (1970) No. 6
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