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Difluorothiophosphoryl Fluorosulfate.

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Hydrogenolytic debenzylation of (3c) in glacial acetic acid
(I'd-charcoal) gave, surprisingly, I-acetyl-6-methylpyrazolo[3,4-b]pyridin-4-01 ( 3 d ) (m.p. 236--239 "C, needles from
ethanol). The I R spectrum of (3d) in KBr showed, not only
an intense, broad carbonyl band, v(C0) = 1655 cm-1 (to be
ascribed to the tautomeric 4-pyridone structure), but also a
carbonyl absorption band for N-CO-CH3 at 1749 cm-1.
The IH-NMR spectrum [in (CD3)2SO] contains a doublet
for the 6-CH3 group at T = 7.69 and a singlet for N-CO-CH3
at 7 = 7.33; however, the N M R spectrum of (3d) in D20
containing N a O D is exactly the same as that of (30), i.e.
there is extremely rapid deuterium exchange aL the N-acetyl
group. Acidifying an alkaline solution of ( 3 d ) precipjtates
6-methyl-lH-pyrazolo[3,4-b]pyridin-4-01(3a) (m.p. 319 to
322"C), which we were also able to obtain, in 95 % yield,
directly from (3.). This was achieved by treatment of (3.1
with sodium in liquid ammonia. Compound (-10) is converted
by POC13 into 4-chloro-6-methyl-1H-pyrazolo[3,4-b]pyridine
(m.p. 154-156OC). The I R spectrum (v(C0) in KBr = 1650
cm-1) shows that in the solid state (30) exists mainly in the
tautomeric 4-pyridone form.
Received: August 30th, 1967
[ Z 614 IE]
German version: Angew. Chem. 79, 981 (1967)
[*I Dr. H. Dorn and Dr. A. Zubek
Institut fur Organische Chemie der Deutschen Akademie der
Wissenschaften zu Berlin
An der Rudower Chaussee
DDR 1199 Berlin-Adlershof (Germany)
[I] Part XI11 of Potentially Cytostatic Compounds. - Part XII:
H . Dorn and M . Schutt, Z. Chem. 7, 276 (1967).
[2] E. CTaylor and J . W . Barton, J. Amer. chem. SOC.81, 2448
(1959); A . Dortzow and M . Siebrechf, Chem. Ber. 93, 1106 (1960);
G . M . Badger and R. P . Rao, Austral. J. Chem. 18, 1267 (1965).
[3] S. Checchi, P. Papini, and M . Rid;, Gazz. chim. ital. 85, 1160
(1955); Chem. Abstr. 50, 10097 (1956); Ss. W.Tabak, J . J.Grandberg, and A . N. Kosst, Chim. geterocikliEeskich Soedinenii 1965,
116; Chem. Zbl. 1966, 37-0992.
[4] H . Dorn and A . Zubek, 2. Chem., in press cf. also
Y. Makisumi, Chem. pharmac. Bull. [Tokyo] 10, 612 (1962);
Chem. Abstr. 58, 13949 (1963).
[ 5 ] ( l c ) was formed in 90% yield o n hydrolysis and decarboxylation of ethyl 5-amino-1-benzylpyrazole-4-carboxylate (m.p.
110 "C), which was obtained from benzylhydrazine and ethyl
2-cyano-3-ethoxyacrylate in boiling ethanol.
Difluorothiophosphoryl Fluorosulfate
trum showed resonances at 7 = - 47.5 [51, assigned to the fluorine bonded t o the sulfur atom, and at p = 27.6 and 57.7
(JP-F,== 1240 Hz) both of which are assigned to the fluorines attached to the phosphorus. The measurements are relative to CCI3F as an internal standard. The area ratio of the
two higher field resonances to that at low field was found to
be 1.8: 1.O. The low-field resonance is divided into a multiplet
due t o coupling with both the phosphorus and the fuorines
attached t o the phosphorus. However, both the high-field
resonances are split into doublets (IF-F,
= 4 Hz). The 31PN M R spectrum showed a triplet centered at -165 Hz (relative to H3P04 used as an internal standard) where J P - F ~=1221 Hz. The N M R spectrum of POF20S02F is similarW
The mass spectrum shows major absorptions [reported as
mass number (species) and relative abundance] as follows:
32(S ") 24.4, 47(POf) 7.4,48(SOf) 4.6, 50(PF') 8.4, 64(S02+)
28.4, 67(SOF+) 31.2, 69(PF2+) 100, 80(S03+) 8.5, 82(PSFi)
3.1, 83(SOFz-'-) 78.5, 98(PSFO+) 9.5, lOl(PSFZ+) 37.9,
117(PSFzO') 7.4, and 20O(PSF20SOzF+) 17.3. The infrared
spectrum shows the following major absorptions (cm-1) :
1493(s), S - 0 asym. str., and 1250(s), S=O sym. str. [31; at
985(vs) and 943(vs, broad) in the P-F and P - 0 str. region [2,41;
862(s), S-F str. [31; 788 (msj, S-0 str., and at ca. 671 (m,
broad), P=S str.
A pure sample of PSF20SOzF was placed into an infrared
gas cell at 10 mm pressure and periodically monitored. After
3 h nearly half the sample remained, after 7 h it was barely
observable and after 24 h it had completely decomposed according to both infrared and mass spectral evidence. The
gaseous decomposition products are SO2 and POF3, present
in ca. 2 : l molar ratio, along with a small quantity of S205F2.
A yellow solid was also formed.
Received: August 19th. 1967
[ Z 61 5 IE]
German version: Angew. Chem. 79, 980 (1967)
[ * ] Dr. Max Lustig
Rohm and Haas Co.,
Redstone Research Laboratories
Huntsville, Alabama (U.S.A.)
[I] This work was carried out under the sponsorship of the U.S.
Army Missile Command, Redstone Arsenal, Alabama, under
Contract No. DAAH01-67-C-0655.
[2] D . D. Des Marteau and G . H . Cady, Inorg. Chem. 5, 1829
I31 M . Lustig, Inorg. Chem. 4, 1828 (1965).
141 A. Miiller, E. Niecke, and 0. Gleinser, Z. Anorg. Allg. Chem.
350, 246 (1967).
(51 For the definition of p see G. Filipovick and G . V . D. Tiers,
J . physic. Chem. 63 761 (1959).
By M a x Lustig [*I
Phosphoryl fluorosulfate, PO(OS02F)3, is the first compound
reported with a fluorosulfate group attached to a phosphorus
atom. This compound decomposes slowly t o the lower fluorosulfates, POF(OS02F)2 and POF20S02F 121 at temperatures
100 "C.
Difluorothiophosphoryl fluorosulfate,
PSF2OSO2F, a colorless compound that is unstable at ambient temperature, has been synthesized in o u r laboratory.
The highest yield of this compound can be achieved by the
slow addition of peroxydisulfuryl difluoride, S206F2, (0.33
mmoles) to difluorothiophosphoryl bromide (0.57 mmole) in
a 50 ml. Pyrex bulb at -45 "C. After the addition was completed the reaction mixture was allowed t o stand for
h and
then allowed to warm slowly t o room temperature. Analysis
revealed that the product mixture contained PSF20S02F
(0.46 mmoles o r 81 % yield), POF3 (0.04 mmoles), SO2 (0.09
mmoles) and PSF3 (0.01 mmole) as well as unreacted PSFZBr
(0.03 mmole). A small quantity of a yellow solid remained in
the reaction vessel. Purification is accomplished by passingthe reaction mixture through cold traps maintained at -95
and -119 "C; the PSF20S02F is retained in the latter.
Immediately after purification of a sample of P S F Z O S O ~ F ,
the molecular weight was determined (vapor density method)
and found to be 197.1 (Calcd: 200.1). The 19F-NMR specAngew. Chem. internat. Edit.
Val. 6 (1967) No. 11
Degradation of 2-Azidoethylene1,l-dicarbonitriles 1'1
By K. Friedrich [*I
Acylmalononitriles ( I ) , R = H (21, CH3 (31, or C6H5 (41, can
be converted into the 2,2-dicyanovinyl chlorides (2) by
phosphorus pentachloride, or, as their sodium salts, by
phosphorus oxychloride. The reactivity of compounds (2) is
comparable with that of carboxylic acid chlorides, in accord
with the principle that structural elements =O and =C(CN)2
are analogous in organic compounds [51. For instance, 2azidoethylene-1,l -dicarbonitriles (3) are obtained smoothly
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difluorothiophosphoryl, fluorosulfate
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