close

Вход

Забыли?

вход по аккаунту

?

N-Fluorosulfonyldichloroamine1.

код для вставкиСкачать
(2) and dimethyl sulfone diimine
of triethylamine.
By Herbert W Roesky[*]
Preparation of (3) by a modified route proved to be more
favorable. Thus compound ( I ) , to which triethylamine has
already been added, is first condensed with N-chlorosulfonylurethane (5) (which is readily accessible from (2)
and methanoli3' and which forms reactive intermediates
with triethylamine[41) to give methoxycarbonylsulfamoyl
dimethyl sulfone diimine ( 6 ) (yield 80%). Brief heating of
( 6 ) in boiling DMF affords ( 3 ) in almost quantitative
yield.
Compounds (3) and ( 6 ) are readily soluble in water and,
because they contain the SO,-NH-CO
group, they can
be titrated as monobasic acidsi3]. Their acid character is
also demonstrated by reaction of (3) and (6) with diazomethane to give the N-methyl compounds j 4 ) and (7).
The structures of ( 3 ) , ( 4 ) , ( 6 ) , and (7) were confirmed
by elemental analysis, molecular weight determinations
(mass spectra), and IR and NMR spectrometric measurements (see Table).
-r-~
M.p ("C)
I
13)
(4)
(61
17)
182 (dec.)
190(dec)
172 (dec) 3320 1754
3010 1742
3290 1740
83
N-Fluorosulfonyldichloroamine"
in the presence
3.70
Attempts to convert the ester j 7 ) into (41 by boiling in
DMF were unsuccessful. This would suggest[51that the
facile condensation of ( 6 ) to form the compound (3)
proceeds via an elimination-addition mechanism involving
a sulfonyl isocyanate intermediate.
Procedure :
A solution of ( 5 ) (3.76 g) in dry methylene chloride (20 ml)
was added dropwise to a vigorously stirred solution of ( I )
(2.0 g) and triethylamine (2.2 g) in dry methylene chloride
(20 ml) within 30 min. After an additional 30 minutes'
stirring, the precipitate was filtered off and washed
thoroughly with methanol; yield 3.9 g (80%) of (6) (can
be recrystallized from acetonitrile). A solution of (6)
(0.75 g) in dry DMF (5 ml) was heated to boiling within
3 min under a current of dry N,. The reaction mixture
was then diluted with anhydrous ethanol (50 ml) and
subsequently cooled in an ice bath for several hours. The
crystals were filtered off under suction and washed with
a little ethanol ;yield 0.6 g (93%)of ( 3 ) (can be recrystallized
from water/isopropanol).
Received: January 8, 1971 [Z 382 IE]
German version: Angew. Chem. 83, 256 (1971)
[l] Aza analogs of sulfonyl compounds, Part 3.-Part 2: M . Haake,
Tetrahedron Lett. 1970, 4449.
[2] J . A . Cogliano and G. Braude, J. Org. Chem. 29, 1397 (1964);
R . Appel, H . W Fehlhaber, D. Hanssgen, and R . Schollhorn, Chem.
Ber. 99, 3108 (1966); R . G . Laughlin and W Yellin, J. Amer. Chem.
SOC 89, 2435 (1967); R . Appel and D. Hanssgen, Chem. Ber. 103,
3733 (1970).
[3] R . GraL Chem. Ber. 96, 56 (1962).
[4] G . M . Atkrns and E . M . Burgess, J. Amer. Chem. Soc. 90, 4744
(1968).
[5] B. E. Hoogenboom, R . Abbott, L. Locarell, and R . L . Hinman,
.I.
Org. Chem. 24, 1983 (1959).
Angew. Chem. internat. Edit. 1 Vol. I0 (1971) 1 No. 4
Perfluorinated inorganic derivatives of dichloroamine are
little known or unstable['* 'I. N-Fluorosulfonyl sulfur
oxide imide reacts with chlorine monofluoride at room
temperature with cleavage of thionyl fluoride to give
N-fluorosulfonyldichloroamine ( I ) in high yield.
FSOZN=S=O+2ClF
+
FSO,NCI,+SOF,
(1)
( I ) is a pale yellow liquid which can be distilled undecomposed at reduced pressure : b. p. 29-3OoC/75 torr. On
standing the compound slowly decomposes with formation
of Cl,, N,, and FS0,Cl. Its identification followed from
elemental analysis and the mass spectrum: m/e 171, 169,
167 (molecular ion); 134,132 (FS0,NCl); 88,86, 84(NCl,);
83 (S0,F) and smaller fragments. The molecular weight
was determined by cryoscopic measurements (in benzene)
to be 165.
The IR spectrum (capillary film between AgCl plates)
shows absorptions at (cm-'): 1458 vs, 1222 vs, 1025 w,
844 vs, 790 vs, 630 m, 588 vs, 522 m, 482 m, 440 s. They are
tentatively assigned to the following vibrations : v,,(SO)
1458, v,(SO) 1222, v(SF) 844, v(SN) and v(NC1) 790, 630,
and 588 cm-'. The "F-NMR spectrum contains a singlet
at 6,= -26.5 (CFCI, as external standard). According to
IR, NMR, and mass spectra the isomeric form ClS0,NClF
is less probable. Compound (1) liberates iodine from
aqueous potassium iodide solution, the first step of the
hydrolysis being formation of hypochlorous acid :
FSO,NCl,
+ HOH
---t
FS0,NClH
(2)
+ HOCl
N-Fluorosulfonylmonochloroamine (2) could be isolated
in the form of its amide by treatment with tetraphenylphosphonium or tetraphenylarsonium chloride :
[(C6H5),P]+ [FSO,NCI]- ; m.p. 200°C (dec.)
[(C,H,),As]+ [FSO,NCl]- ; m.p. 154°C (dec.)
Both salts are colorless and are soluble in acetone and
methanol.
Experimental :
FS0,NSO (0.1 mole) is placed in a 100ml two-necked
quartz flask fitted with a delivery tube, refluxing condenser,
and T-piece for purging with dry nitrogen. ClF (0.25 mole)
is fed into the flask, the internal temperature of which is not
allowed to increase beyond 30°C. Finally, the flask is
purged with nitrogen and the liquid phase is fractionally
distilled twice at 75 torr. Yield of ( I ) : 13.5 g (81%). The
highest boiling fraction contained, in addition to FS0,NSO
and ( I ) , a compound which according to the 19F-NMR
spectrum (J,-,= 13 Hz) could be FSO,NS(O)ClF, but it
could not be isolated in pure form.
Received: January 11, 1971 [Z 353 IE]
German version: Angew. Chem. 83, 252 (1971)
[*] Univ.-Doz. Dr. H. W. Roesky
[I]
and
[2]
[3]
Anorganisch-chemisches Institut der Universitat
34 Gottingen, Hospitalstr. 8-9 (Germany)
Part 36 of "Sulfur-Nitrogen Compounds"; Part 38: H . W Roesky
S. Tutkunkardes, Chem. Ber., in press.
B. Sukornick, R . F. Stahl, and J . Gordon, Inorg. Chem. 2,875 (1963)
A. F . C l l f f r d and G. R . Zeilenga, Inorg. Chem. 8,979 (1969).
265
Документ
Категория
Без категории
Просмотров
1
Размер файла
126 Кб
Теги
fluorosulfonyldichloroamine1
1/--страниц
Пожаловаться на содержимое документа