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Inner Phosphonium and Ammonium Dithiophosphonates.

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The position of the tosyl substituent in (3) was proved by
tosylation of I-methyl-3-pyrazolidone to an isomer of (Sa),
i.e. 2-(p-toluenesulfonyl)-l-methyl-3-pyrazolidone,
m.p. 111
to 113 "C,v(CO) = 1744 cm-l,v(SOp sym)= 1159,1175 cm-1,
v(S02 asym) = 1359 cm-1.
With liquid sulfur dioxide the compounds (2) yield tributylphosphine sulfide, sulfur, and the corresponding phosphonic
anhydride (5) [21, whereas with an excess of tributylphosphine
+
Received: May 9th, 1966
[ Z 232 IE]
German version: Angew. Chem. 78, 676 (1966)
111 Part 7 of Redox Cleavage of Sulfonarnides. - Part 6: H.Dorn,
G. Hilgetag, and A . Zubek, Chern. Ber. 99, 183 (1966).
[2] S. Ruhemann and K . J. P . Orton, J. chern. SOC.(London)
1895, 1002; L. Knorr, Ber. dtsch. chern. Ges. 29, 253 (1896).
[3] H . Dorn and A. Zubek, Z. Chern. 5 , 457 (1965).
[4] F. Stolz, Ber. dtsch. chern. Ges. 28, 630 (1895); H . Dorn,
A. Zubek, and G . Hilgetag, Chern. Ber. 98, 3377 (1965).
+ 1/4 SS
+
(3)
(15 hr at 80 "C in benzene) they give arylcyclophosphines (6)
and tributylphosphine sulfide.
go
&
-
By Doz. E. Fluck[ll and H. Binder
Anorganisch-Chemisches Institut,
Universitat Heidelberg (Germany)
boiling in a n Nz-stream, is treated with 2 moles of tri-n-butyl(I), 5.9 g of (n-C4H&P,
phosphine (e.g. 5 g of [C,&PS&
and 50 ml of benzene), complete solution occurs in ca.
5 minutes. When the solution is cooled, or if necessary
concentrated, colorless crystals separate which can be
obtained analytically pure by washing with a little benzene.
The resulting compounds (2) are t o be considered as inner
phosphonium salts stabilized by resonance. They are stable
in air, and cryoscopic molecular-weight determinations in
benzene, bromoform, and nitrobenzene indicate that they
are monomeric. Their 31P-NMR spectra include two doublets with coupling constants characteristic of P-P linkages.
9,s 9
R-PNS;P-R
+ 2 (n-C4Hg)3P
I
C6HSp-CH90-CrjH4p-CzHjO-C6H4-
-
I
97-98
:-87
+
R-P - P ( n -
Inner Phosphonium and Ammonium
Dithiophosphonates
If a suspension of a perthiophosphonic anhydride in benzene,
+ (RPO,),
(n-C&)sP=S
l / n (RP)n
+
2 (n-C4Hg)sP=S
f 61
Investigation of the reaction of amines and phosphines with
phosphonic anhydrides are in progress.
Received: April 21st. revised May 9th, 1966
[Z 234 IE]
German version: Angew. Chem. 78, 677 (1966)
[I] We thank the Landesgewerbearnt Baden-Wurtternberg for
financial support.
[2] E. Ffuck and H. Binder, Angew. Chern. 77, 381 (1965); Angew. Chem. internat. Edit. 4 , 359 (1965).
Novel Purine Syntheses
By Prof. W. Pfleiderer and H.-U. Blank
Institut fur Organische Chemie,
Technische Hochschule Stuttgart (Germany)
2 R-
- 60.0; - 6.8
- 60.0; - 7.4
- 60.9; - 6.8
1
118
109
108
Strongly basic tertiary amines react like phosphines with
perthiophosphonic anhydrides, giving inner ammonium
salts. If, for instance, phenylperthiophosphonic anhydride is
boiled for 1 hour with 10 moles of pyridine and the cooled
solution is treated with benzene to turbidity, the crystalline
pyridine N-phenyldithiophosphonic betaine (3) separates
1.0 ppm; yield 80-85 %).
(m.p. 122-125OC; 8p = 82.2
In the dehydrogenating cyclization of 4-amino-5-benzylideneamino-1,3-dimethyluracilto 8-phenyltheophylline Traube [11
found a synthesis of imidazole derivatives which was later
used mainly for preparation of benzimidazoles [21. If N4alkyl - 5 - benzylideneamino - 1,3-dimethyluracil-4-aminesare
chosen as starting materials and cyclized in nitrobenzene,
the main products are not 9-alkyl-8-phenyltheophyllines,
but instead 7-benzyltheophylline or its 8-alkyl derivatives, in
analogy with the cyclization of 3-substituted or 1,3-disub[31.
stituted 6-alkylamino-5-nitrosouracils
R'
;@2
C.&-P-N
(3)
SQ
This compound reacts with tributylphosphine with elimination of pyridine and formation of compound (2).
The inner phosphonium salts (2) react with primary and
secondary aliphatic amines (spontaneously at room temperature in a pressure tube) with fission of the P-P bond,
yielding ammonium phosphonoamidodithioates (4) and tributylphosphine.
(2)
+
2 CH3NHz
-+
s
R-P-NHCH3
H38CH3
(4)
666
+
(n-C4Hg)3P
k
(a)
(b)
Ic)
(d)
H
H
H
C6HS
H
H
CI
H
NO2
H
H
H
40
(3)
12
48
51
50
Angew. Chem. internat. Edit. / Vol. 5 (1966)
/ No. 7
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