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Geometric Isomerism in Cyclic Five- and Six-Membered Monothiophosphoric Acid Derivatives.

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Geometric Isomerism in Cyclic Five- and
Six-Membered Monothiophosphoric
Acid Derivatives * * I
By M . Mikolajczyk and H . M . Schiebel[*I
The sodium salt of 2-hydroxy-4-methyl-l,3,2-dioxaphosphorv-inane-2-thione (3) (sodium l-methyltrimethylenethionophosphate) was prepared in 92% yield by alkaline hydrolysis of the chloride, according to the method of Edmundson [6J. The isomers were separated by fractional crystallization.
Monothiophosphoric acids ( A ) are chiralic compounds with
the phosphorus atom as asymmetric center [ I ] . Because of
their high reactivity they prove most suitable as starting
materials for the synthesis of other optically active phosphorus compounds containing P=O- or P=S-groupings [ 1 , 2 1 .
We report here o n the geometric isomerism of cyclic monothiophosphoric acid derivatives [31 which occurs when the
molecule containslat least one asymmetric center a t a ring
carbon atom.
The cis and trans isomers of compound (3) are likewise
distinguishable from each other in their 1H- and 31P-NMR
6 = 1.28 ppm (CH3, qf
= 1.27 pprn (CH3, q)
(measured in D 2 0 with DSS as internal standard)
J H - C H ~ = 6.2 Hz
J H - C H ~ = 6.2 Hz
JP-O-CH-CH~ = 1.7 Hz
JP-O-CH-CH~ = 2 Hz
631P = -120ppm
83tp = -112.9 ppm
(measured in H20 with 80":,H3P04 as external standard)
(Two signals,
(Two signals,
separated by 48 Hz)
separated by 60 Hz)
(For assignment of data to the cis and trans forms see [7].)
Good results were obtained in the elemental analyses of all
the compounds investigated. The 31P-NMR measurements
were carried out with a Perkin Elmer R 10 spectrometer in
combination with a Northern Scientific NS 544 Digital
Memory OsciIloscope.
Received: April 2, 1969
[Z 992a 1EJ
German version: Angew. Chem. 81, 494 (1969)
(bl Icl
I I 1
la1 From n-propanallether.
[*] Doz. Dr. M. Mikolajczyk
-160 [dl
[bl Measured in HzO.
[dl Two signals
[cl Mixture of cis and trans forms.
By reaction of the cyclic thiophosphoryl chlorides ( I ) [41
with imidazole in tetrahydrofuran, we were able to prepare
the corresponding imidazolides, which, o n account of their
instability, were converted without isolation into the imidazolium salts (2) of thiophosphoric acids by reaction with
As is to be expected, the imidazolium propylenethionophosphate (2b) prepared in this way is a mixture of the cis and
trans isomers 151.
cis- (2b)
The IH-NMR spectrum at 100 MHz shows two doublets of
equal intensity a t 1.40 and 1.41 ppm (JH-cH, = 6.1 Hz)
(measured in DzO with sodium 2-trimethylsilylpropanesulfonate as internal standard), which can be ascribed to the
protons of the methyl group.
I n the 31P-NMR spectrum (measured in H 2 0 with 80%
phosphoric acid as external standard), two signals appear at
-160.0 ppm which are separated by about 22 Hz. We have
been able to obtain one isomer in the pure state [m.p. 122 to
125 "C, 6 = 1.41 ppm (CH3)I by repeated recrystallization of
the mixture from n-propanollether. The other isomer can be
isolated from the mother liquor in abont 90% purity (m.p.
78.5-83 "C). Assignment of the cis and trans forms has not,
as yet, been possible.
Angew. Chem. internat. Edit. J Vol. 8 (1969) 1 No. 7
Institute of Organic Chemistry, Polish Academy of Sciences
t 6 d i 40, Zwirki 36 (Poland)
Dr. H.M. Schiebel
Institut fur Molekulare Biologie, Biochemie und Biophysik
33 Braunschweig-Stockheirn, Mascheroder Weg 1 (Germany)
[**I M. M. thanks the Max-Planck-Institut fur experimentelle
Medizin (Gottingen) for a one-year stipend.
[l] R. F. Hudson and M . Green, Angew. Chem. 75, 47 (1963);
Angew. Chem. internat. Edit. 2, 11 (1963); H. E. McEwen,
Topics in Phosphorus Chemistry 2, 1 (1965); J. Michalski, Bull.
SOC.chim. France 4, 1109 (1967).
[2] J. Michalski, M . Mikolajczyk, and J . Omelanczuk, Tetrahedron Letters 1965, 1779; J . Michalski, M . Mikolajczyk, B.
Mlotkowska, and J . Omelanczuk, Tetrahedron 25, 1743 (1969).
(31 F. Eckstein and H. Gindl, Chem. Ber. 101, 1670 (1968);
F. Ecksfein, FEBS-Letters 2, 85 (1968).
[4] Houben- Weyl: Methoden der organischen Chemie Vo!. XIIIZ.
Thieme-Verlag, Stuttgart 1964, p. 610. The chloride ( l c ) , m.p.
62-65 "C, was obtained from 2-mercapto-4,4,5,5-tetramethyl1,3,2-dioxaphospholane-2-thione
and phosphorus pentachloride.
[ 5 ] We designate the thiophosphoric acid having methyl group
and sulfur atom cis to each other as the cis-acid.
[6] R. S.Edmundson and A . J. Lambie, J . chem. SOC.(London)
B 1967, 577.
[7] M . Mikolajczyk, Angew. Chem. 81, 495 (1969); Angew.
Chem. internat. Edit. 8, 511 (1969).
Stereospecific Synthesis of cis-2-Hydroxy-4-methyl1,3,2-dioxaphosphorv-inane-2-thione
1* * 1
By M . Mikolajczyk [*I
The sodium salt of 2-hydroxy-Cmethyl-1,3,2-dioxaphosphorv-inane-2-thione (sodium l-methyltrimethylenethionophosphate)
can exist in two geometrical forms, which are
distinguishable from each other in their 1H- and their 31PN M R spectra. In oder to assign the N M R data to the isomers
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acid, cyclic, monothiophosphoric, isomerism, membered, five, six, derivatives, geometrija
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