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Isomeric morpholine derivatives of ga -sulfanuric chloride
IHORG.
HUCL.
CHEM.
LETTERS.
ISOMERIC
V°l. 2,
MORPHOLINE
I~. 165-168,
1966.
Pergamon Pre=s
Ltd.
Printed
In
Great
Britain.
~ERIVATIVES (F ~_-SULFANURIC CHLORIE~
Amedeo Failli, Marlene A. Kresge, Christopher W. Allen, and Therald Moeller Noyes Chemical Laboratory, University of Illinois~ Urbane, Illinois, U.S.A.
(Received 7/day •966) The well-kno~rn s o l v o ] ~ i c
substitution
reactions
of the tr~eric
phospho-
nitrilic halides, (NPX2)s, suggest that parallel behavior may be expected with the isoelectronic sulfanuric halides, (NSGX) S.
However, preliminary studies
involving ~_-sulfanuric chloride, the most readily accessible of the trimeric sulfanuric halides, indicate either solvolysis by ammonia followed by polymerization to yield melam and melem analogs (1) or ring cleavage with morphollne to form N_~N'-dlmorpholidosulfamide (2), but give no evidences for the formation of readily isolable substitution products. We have now established that under controlled conditions morphollne can react with ~_-sulfanuric chloride without ring cleavage and with the formation of colorless, crystalline trimorpholido derivatives,
with benzene as solvent
and a sufficient excess of morpholine present to function as a hydrogen chloride acceptor, a trlmorpholido compound (I), melting at 171-172@C. (uncorr.) after recrystallization from acetonitrile and absolute ethanol, was obtained in 40-50% initial yield.
With benzene as solvent and a sufficient quantity of
trlethylamine present to serve as a preferential hydrogen chloride acceptor, a mixed product (melting point 160-162°C. ) was obtained in 45-54% initial yield. From this mixture, a second trimorpholido compound (I_~I), melting at 196-197@C. (uncorr.), was separated from I by recrystallization from absolute ethanol in 3~-49% overall yield.
With acetonitrile as solvent and excess morphollne pres-
ent, compound I_IIwas obtained in ca. 56% overall yield.
Each reaction was car-
ried out by adding a solution of ~_-sulfanuric chloride (2) in theappropriate solvent dropwise over a period of 1-1.5 hrs. to a well-stirred and externally
165
166
ISOMERIC MORPHOLINE DERIVATIVES
Vol. 2, No. 6
cooled (by ice-water) solution of morpholine (or morpholine plus triethylamine) in the same solvent, the entire reaction system being protected from moisture. The reaction mixture was then allowed to warm to room temperature, an additional 5-7 hrs., and permitted to stand for ca. 20 hrs. tated amine hydrochloride and solvent ~ r e and evaporation in vacuo.
stirred for
The precipi-
removed, respectively, by filtration
The oily residues ~ r e
rendered crystalline by
treatment with absolute ethanol and the products ultimately separated and purified by crystallization. Ana__~l. Calcd. for CIeHa4OeNeSs:
C, 32.41; H, 5.44; N, 18.90; S, 21.63; Mol. wt., 444.6.
Found for I (m.p., 171-172°C.):
C, 32.37; H, 5.89; N, 18.93; S, 21.86; Mol. wt., 403.*
Found for I_!I (m.p., 196-197°C. ):
C, 32.58; H, 5.47; N, 18.38; S, 21.76; Mol. wt., 438.**
Neither _I nor I I is extensively soluble in acetone, dioxane, diethyl ether, tetrahydrofuran, ethanol or acetonitrile.
nitrobenzene,
or pyridine.
Each dissolves in absolute
Compound I is soluble in water but not in anhydrous
benzene; compound I I is soluble in anhydrous benzene but n ~ in water.
The
infrared spectra, as recorded for benzene solutions (II only) or potassium bromide disks with a Perkin-Elmer Model 21 double-beam instrument using sodium chloride optics, of the two compounds are similar (Table 1), as are those of ~- and ~-sulfanuric chlorides (2).
The large number of morpholine bands pre-
vents absolute identification of the S=O stretching frequency, which appears con~uonly in the ]250-1300 cm.-i region (3)-
The bands around 1075 era.-i in-
dicate S-N ring vibrations, as noted at lllO cm.-i for ~-sulfanuric chloride (2) and at llOO-1200 cm. -i for "cis" trimeric sulfanuric fluoride and its derivatives (4).
Decrease in frequency parallels weakening of the S-N bond by
decreasing polarization of the sulfur atoms by the exocyelic groups. * Cryoscopically in camphor.
** Osmometrically in benzene.
The
Vol. 2, No. 6
ISOMERIC MORPHOLIHE DERIVATIVES
167
TABLE 1 Infrared Spectra of Trimorpholido Derivatives
Compound
Frequency,
I
3130(m)* 2980(m) 2860(m) 2480(w)
1325(sh) 1305(sh) iR92(m)
ll08(s) 1075(s) 1055(s) lO16(w)
897(w ) 873(m) 855(w) 814(m)
1455(m)
~58(sh) IP42(s) 1228(s) i196(s)
985(s) 943(s)
767(m) 750(m) 715(s)
ll05(s) 1075(s) lO15(w)
870(w) 851(m) 826(s)
1355(w) 2970(w) 2860(w)
I_!
om.-1
1332(w) 1295(m)
1455(m) 1275(sh) 1258(s) 1216(w)
1395(w) 1355(w)
* w, weak; m, medium;
800(sh) 967(m) 942(s) 915(sh)
762(w) 750(v) 723(s) 700(sh)
s, strong; sh, shoulder.
strong bands at 942-948 cm. -~ are probably assignable to exocyclic S-N vibrations since they are absent in the spectra of the halides.
The complexity of
the S-N spectra in the 715-767 cm. -~ region (3) is probably a consequence of the presence of both exo- and endocyclic S-N bonds.
The x-ray diffraction
data, as obtained for pounders with a Hayes camera of 139.3-cm. CuK~ radiation,
diameter and
show that I and I I are closely related but definitely differ-
ent c ryst allographi c ally. It is impossible,
on the basis of the data recorded, to assign a defini-
tive configuration to either isomer.
The s~m~larities between the infrared
spectra, particularly in the light of those already obtained (2~4), suggest differences
in the orientation of substituents
than differences
on the sulfanuric ring rather
in the conformation of the ring itself.
not inconsistent with this possibility,
The x-ray data are
nor is the fact that compound I
168
ISOMERIC MORPHOLINE DERIVATIVES
Vol. 2, No. 6
TABLE R Interplanar Spacings (d) in Angstroms
Ccc~ound _I 1,80(vw)* 1.85(vw) 1.93(vw) 2.G2(w) 2.15(w) 2.24(w) 2.30(w) 2.43(w) 2.54(w) 2.66(w)
2.76(w) 2.83(w) 2.89(w) 2.95(vw) 3.13(m) 3.39(s) 3.60(w) 3, 80(m) 4.05(w) 4.24(vs)
Compound I__II 4.37(m) 4.81(vs) 5.O7(w) 5.61(m) 6.18(m) 6.83(vs) 8.60(m) 12.35(w)
1.86(v~) 1.93(w) 2.00(vw) 2.09(w) 2.15(vw) 2.20(m) 2.27(w) 2.34(m) 2.43(m) 2.59(m)
2.71(w) 2.88(vw) 3.04(m) 3.26(m) 3.47(m) 3.62(.w) 3.74(w) 3.88(m) 4.O5(m) 4.39(s)
4.76(s) 5.06(w) 5.25(m) 5.40(m) 5.68(vw) 5.81(w) 6.05(m) 6.91(m) 7.42(vs) 8.38(w) 9.79(w)
vw, very ~ak; w, weak; m, medium; s, strong; vs, very strong. results under much less polar conditions than does compound I I.
Detailed
crystal structure evaluation of the two products is in order. Acknowledgment. -- This investigation was supported by Army Research Office Grants ~-124-ARO(D)-35 and USDA-AR0(D)-31-124-GT19. REFERENCES i.
M. BECKE-GOEHRING, Developments in Inorganic Polymer Chemistry, M. F. Lappert and G. J. Lelgh, Eds., p. ll6.
Elsevier, New York (1962).
2.
A. VANDI, T. MOELLER, AND T. L. BROWN, Inorg. Chem. 2, 899 (1956).
3.
K. C. SCHREIBER, Anal. Chem. 21, 1168 (1949).
4.
T. MOETT~ and A. OUCHI, J. Inorg. Nucl. Chem. (in press).
HUCL.
CHEM.
LETTERS.
ISOMERIC
V°l. 2,
MORPHOLINE
I~. 165-168,
1966.
Pergamon Pre=s
Ltd.
Printed
In
Great
Britain.
~ERIVATIVES (F ~_-SULFANURIC CHLORIE~
Amedeo Failli, Marlene A. Kresge, Christopher W. Allen, and Therald Moeller Noyes Chemical Laboratory, University of Illinois~ Urbane, Illinois, U.S.A.
(Received 7/day •966) The well-kno~rn s o l v o ] ~ i c
substitution
reactions
of the tr~eric
phospho-
nitrilic halides, (NPX2)s, suggest that parallel behavior may be expected with the isoelectronic sulfanuric halides, (NSGX) S.
However, preliminary studies
involving ~_-sulfanuric chloride, the most readily accessible of the trimeric sulfanuric halides, indicate either solvolysis by ammonia followed by polymerization to yield melam and melem analogs (1) or ring cleavage with morphollne to form N_~N'-dlmorpholidosulfamide (2), but give no evidences for the formation of readily isolable substitution products. We have now established that under controlled conditions morphollne can react with ~_-sulfanuric chloride without ring cleavage and with the formation of colorless, crystalline trimorpholido derivatives,
with benzene as solvent
and a sufficient excess of morpholine present to function as a hydrogen chloride acceptor, a trlmorpholido compound (I), melting at 171-172@C. (uncorr.) after recrystallization from acetonitrile and absolute ethanol, was obtained in 40-50% initial yield.
With benzene as solvent and a sufficient quantity of
trlethylamine present to serve as a preferential hydrogen chloride acceptor, a mixed product (melting point 160-162°C. ) was obtained in 45-54% initial yield. From this mixture, a second trimorpholido compound (I_~I), melting at 196-197@C. (uncorr.), was separated from I by recrystallization from absolute ethanol in 3~-49% overall yield.
With acetonitrile as solvent and excess morphollne pres-
ent, compound I_IIwas obtained in ca. 56% overall yield.
Each reaction was car-
ried out by adding a solution of ~_-sulfanuric chloride (2) in theappropriate solvent dropwise over a period of 1-1.5 hrs. to a well-stirred and externally
165
166
ISOMERIC MORPHOLINE DERIVATIVES
Vol. 2, No. 6
cooled (by ice-water) solution of morpholine (or morpholine plus triethylamine) in the same solvent, the entire reaction system being protected from moisture. The reaction mixture was then allowed to warm to room temperature, an additional 5-7 hrs., and permitted to stand for ca. 20 hrs. tated amine hydrochloride and solvent ~ r e and evaporation in vacuo.
stirred for
The precipi-
removed, respectively, by filtration
The oily residues ~ r e
rendered crystalline by
treatment with absolute ethanol and the products ultimately separated and purified by crystallization. Ana__~l. Calcd. for CIeHa4OeNeSs:
C, 32.41; H, 5.44; N, 18.90; S, 21.63; Mol. wt., 444.6.
Found for I (m.p., 171-172°C.):
C, 32.37; H, 5.89; N, 18.93; S, 21.86; Mol. wt., 403.*
Found for I_!I (m.p., 196-197°C. ):
C, 32.58; H, 5.47; N, 18.38; S, 21.76; Mol. wt., 438.**
Neither _I nor I I is extensively soluble in acetone, dioxane, diethyl ether, tetrahydrofuran, ethanol or acetonitrile.
nitrobenzene,
or pyridine.
Each dissolves in absolute
Compound I is soluble in water but not in anhydrous
benzene; compound I I is soluble in anhydrous benzene but n ~ in water.
The
infrared spectra, as recorded for benzene solutions (II only) or potassium bromide disks with a Perkin-Elmer Model 21 double-beam instrument using sodium chloride optics, of the two compounds are similar (Table 1), as are those of ~- and ~-sulfanuric chlorides (2).
The large number of morpholine bands pre-
vents absolute identification of the S=O stretching frequency, which appears con~uonly in the ]250-1300 cm.-i region (3)-
The bands around 1075 era.-i in-
dicate S-N ring vibrations, as noted at lllO cm.-i for ~-sulfanuric chloride (2) and at llOO-1200 cm. -i for "cis" trimeric sulfanuric fluoride and its derivatives (4).
Decrease in frequency parallels weakening of the S-N bond by
decreasing polarization of the sulfur atoms by the exocyelic groups. * Cryoscopically in camphor.
** Osmometrically in benzene.
The
Vol. 2, No. 6
ISOMERIC MORPHOLIHE DERIVATIVES
167
TABLE 1 Infrared Spectra of Trimorpholido Derivatives
Compound
Frequency,
I
3130(m)* 2980(m) 2860(m) 2480(w)
1325(sh) 1305(sh) iR92(m)
ll08(s) 1075(s) 1055(s) lO16(w)
897(w ) 873(m) 855(w) 814(m)
1455(m)
~58(sh) IP42(s) 1228(s) i196(s)
985(s) 943(s)
767(m) 750(m) 715(s)
ll05(s) 1075(s) lO15(w)
870(w) 851(m) 826(s)
1355(w) 2970(w) 2860(w)
I_!
om.-1
1332(w) 1295(m)
1455(m) 1275(sh) 1258(s) 1216(w)
1395(w) 1355(w)
* w, weak; m, medium;
800(sh) 967(m) 942(s) 915(sh)
762(w) 750(v) 723(s) 700(sh)
s, strong; sh, shoulder.
strong bands at 942-948 cm. -~ are probably assignable to exocyclic S-N vibrations since they are absent in the spectra of the halides.
The complexity of
the S-N spectra in the 715-767 cm. -~ region (3) is probably a consequence of the presence of both exo- and endocyclic S-N bonds.
The x-ray diffraction
data, as obtained for pounders with a Hayes camera of 139.3-cm. CuK~ radiation,
diameter and
show that I and I I are closely related but definitely differ-
ent c ryst allographi c ally. It is impossible,
on the basis of the data recorded, to assign a defini-
tive configuration to either isomer.
The s~m~larities between the infrared
spectra, particularly in the light of those already obtained (2~4), suggest differences
in the orientation of substituents
than differences
on the sulfanuric ring rather
in the conformation of the ring itself.
not inconsistent with this possibility,
The x-ray data are
nor is the fact that compound I
168
ISOMERIC MORPHOLINE DERIVATIVES
Vol. 2, No. 6
TABLE R Interplanar Spacings (d) in Angstroms
Ccc~ound _I 1,80(vw)* 1.85(vw) 1.93(vw) 2.G2(w) 2.15(w) 2.24(w) 2.30(w) 2.43(w) 2.54(w) 2.66(w)
2.76(w) 2.83(w) 2.89(w) 2.95(vw) 3.13(m) 3.39(s) 3.60(w) 3, 80(m) 4.05(w) 4.24(vs)
Compound I__II 4.37(m) 4.81(vs) 5.O7(w) 5.61(m) 6.18(m) 6.83(vs) 8.60(m) 12.35(w)
1.86(v~) 1.93(w) 2.00(vw) 2.09(w) 2.15(vw) 2.20(m) 2.27(w) 2.34(m) 2.43(m) 2.59(m)
2.71(w) 2.88(vw) 3.04(m) 3.26(m) 3.47(m) 3.62(.w) 3.74(w) 3.88(m) 4.O5(m) 4.39(s)
4.76(s) 5.06(w) 5.25(m) 5.40(m) 5.68(vw) 5.81(w) 6.05(m) 6.91(m) 7.42(vs) 8.38(w) 9.79(w)
vw, very ~ak; w, weak; m, medium; s, strong; vs, very strong. results under much less polar conditions than does compound I I.
Detailed
crystal structure evaluation of the two products is in order. Acknowledgment. -- This investigation was supported by Army Research Office Grants ~-124-ARO(D)-35 and USDA-AR0(D)-31-124-GT19. REFERENCES i.
M. BECKE-GOEHRING, Developments in Inorganic Polymer Chemistry, M. F. Lappert and G. J. Lelgh, Eds., p. ll6.
Elsevier, New York (1962).
2.
A. VANDI, T. MOELLER, AND T. L. BROWN, Inorg. Chem. 2, 899 (1956).
3.
K. C. SCHREIBER, Anal. Chem. 21, 1168 (1949).
4.
T. MOETT~ and A. OUCHI, J. Inorg. Nucl. Chem. (in press).