1499
V. A. Pinchuk et al. • Chemistry of the 1.3,5-Triaza-2-phosphorin-4.6-diones
2-Phenyl-2-(p-tolylthio)-l ,3,5-trim ethyl-l,3,5-
triaza-4,6-dione-2-phosphorinonium
hexachloroantimonate (4a)
C n H 14N 30 2P (251.2)
Calcd
C 52.59 H 5.62 N 16.73%,
Found C 52.10 H 5.63 N 16.64%.
A
solution of PhPC l2 (0.82 g, 4.6 m m ol) in 3
Alternate synthesis o f 2-phenyl-2-(p-tolylthio)-
1,3,5-trim ethyl-l ,3,5-triaza-4,6-dione-2-
phosphorinonium hexachloroantimonate (4a)
ml of dichlorom ethane was added dropw ise with
stirring at -20°C over 15 min to a solution of 3
(1.56 g, 4.6 m m ol) in 3 ml of dichlorom ethane. The
solvent and the volatile by-products of the reac-
tion were rem oved i.v., and 5 ml of dichlorom eth-
ane was added to the oily residue. To this solution
a solution of SbCl5 (1.4 g. 4.6 m m ol) in 5 ml of
dichlorom ethane was added dropwise with stirring
at -60°C over 30 min. The solvent was rem oved i.v.
to 1/2, and the product was obtained as colorless
crystals after leaving the resulting solution at
-20°C for 48 h. Yield 2.87 g (88% ), m.p. >200°C.
'H NM R (C D ,C N ):
Hz, p-H^CC6H 4), 2.82 (s, ((0:)C )->N C //,), 3.06 (d,
3J(H P ) 11.26 Hz, P (N C //,)2), 7.37-8.18 (m,
C6/ / 4, C6/ / 5). - 13C N M R (C D ,C N ): 6 = 21.32 (s,
/7-H ,C C6H 4), 31.50 (s, ((0 :)C )2N C H 3), 32.07 (d.
2J(C P ) = 6.55 Hz, P (N C H ,)2), 117.81-139.89 (m,
C6H 4, C6H .), 145.76, 149.43 (d. 2J(C P ) = 3.70 Hz,
A solution of p-tolylsulfenyl chloride (2) (0.2 g,
1.26 m m ol) in 3 ml of dichlorom ethane was added
dropw ise with stirring at 0°C over 15 min to a solu-
tion of 6 (0.3 g, 1.26 m m ol) in 3 ml of dichloro-
m ethane. The solvent was rem oved i.v. and to the
residue 5 ml of dichlorom ethane was added. To
this solution a solution of SbCl5 (0.4 g, 1.26 m m ol)
in 3 ml of dichlorom ethane was added dropwise
with stirring at -60°C over 15 min. H alf of the
solvent was rem oved i.v. and the product was o b -
tained as colorless crystals on leaving the resulting
solution at -20°C for 48 h; its physical and spectro-
scopic data were identical to those of 4a obtained
as above.
= 2.41 (d. J(H P ) = 2.65
=
2-Phenyl-1,3,5-trimethyl-l ,3,5-triaza-l',10-dioxa-
8,9-perchlorobenzo-2P-phosphaspiro-
[4.5]-decan-4,6-dione (7)
2.28 Hz, (C (:0 )).
69.0. FAB-M S (NBA ): m /z (% ): 374 (100)
-
31P N M R (C D ,C N ): d =
-
[C ation]+; 91 (38) [H3CC 6H 4]+, 77 (40) [Ph]+.
A solution of PhPC l2 (1 g, 5.6 m m ol) in 5 ml of
dichlorom ethane was added dropwise with stirring
at -20°C over 15 min to a solution of 3 (2.2 g, 5.6
m m ol) in 5 ml of dichlorom ethane. The solvent
was rem oved i.v. and to the oily residue 10 ml of
toluene was added. To the resulting solution a so-
lution of tetrachloroorthobenzoquinone (1.37 g,
5.6 m m ol) in 5 ml of toluene was added dropwise
with stirring at 0°C during 15 min. The reaction
m ixture was heated for 2h at 110°C. The product
C 18H 21Cl6N ,0 2PSSb (708.9)
[C,«H21N3Ö 2PS]+ (374.4)
Calcd
C 30.50 H 2.99 N 5.93% ,
Found C 29.97 H 2.89 N 5.90% .
2-Phenyl-1,3,5-trim ethyl-l ,3,5-triaza-2V-
phosphorin-4,6-dione (6)
A
m ixture of 1,3,5-trim ethylbiuret (3.1 g, 21.4
was precipitated as
a colorless crystalline sub-
m m ol), PhPCl2 (3.8 g, 21.4 m m ol), and triethyl-
am ine (2.2 g, 21.8 m m ol) in 25 ml of toluene was
heated with stirring at 80°C for 3 h. The solvent
was rem oved i.v. and 15 ml of diethyl eth er and
15 ml of toluene w ere added to the residue. The
precipitate was filtered off and the solvent was re-
m oved from the filtrate i.v. To the residue 20 ml
of light petroleum eth er (b.r. 30-40°C ) was added
and the product was obtained as a slightly yellow
am orphous substance on cooling this solution to
-20°C. Yield 3.4 g (63% ), m.p. 67-68°C .
stance on cooling the reaction m ixture to room
tem perature, and was recrystallized from the sam e
solvent. Yield 1.6 g (57% ), m.p. 159-160°C .
'H N M R (C D C l,): <5 = 2.92 (d. V (H P ) = 9.76
Hz, P (N C //,)2), 3.34 (s, ((O :)C ),N C //0 , 7.48-7.59
(m, C 6/ / 5); 31P N M R (CDC13): (3 = -29.5.
C 17H 14C14N ,0 4P (497.1)
Calcd
C 41.08 H 2.84 N 8.45% ,
Found C 41.23 H 2.81 N 8.53%.
'H NM R (CD C L): 6 = 3.03 (s, ((0 :)C )2N C //,),
3.18 (d, -V(HP) = 12.16 Hz. P(N C H ^ ), 7.14-7.37
X -R ay Crystal Structure D eterm inations
For a sum m ary of the crystal data: see Table I.
Data collection and reduction: Crystals were
m ounted on glass fibres in inert oil and transferred
to the cold gas stream of the diffractom eter (Stoe
STA D I-4 for 4a, Siem ens P4 for 7, both with LT-2
(m. C6//,).
((0:)C)->NCH3), 31.02 (d, 27(C P
-
13C N M R (C D C h): 29.79 (s,
6.51 Hz,
)
=
P (N C H ,),), 120.43-137.17 (m, Q H ,), 150.22 (d,
2J(C P) = 8.72 Hz, (C (:0 )).- 31P N M R (CDC1,):
6 = 70.6.
Unauthenticated
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