α-(N-Sulfonylamino)alkylphosphonates

Article abstract of DOI:10.1023/A:1016013723887

α-(N-Sulfonylamino)alkyl phosphites, which are intermediate products in the reactions of the corresponding hydroxy derivatives with diethyl phosphorochloridite, undergo in situ phosphorotropic rearrangement to give C-phosphorylated products.

Full text of DOI:10.1023/A:1016013723887

Russian Chemical Bulletin, International Edition, Vol. 51, No. 5, pp. 897—898, May, 2002
897
αꢀ(NꢀSulfonylamino)alkylphosphonates
ꢀ
F. I. Guseinov and R. N. Burangulova
Kazan State Technological University,
15 ul. K. Marksa, 420068 Kazan, Russian Federation.
Fax: +7 (843 2) 76 1464. Eꢀmail: eltos@kai.ru
αꢀ(NꢀSulfonylamino)alkyl phosphites, which are intermediate products in the reactions
of the corresponding hydroxy derivatives with diethyl phosphorochloridite, undergo in situ
phosphorotropic rearrangement to give Cꢀphosphorylated products.
Key words: αꢀ(Nꢀsulfonylamino)alkyl phosphites, αꢀ(Nꢀsulfonylamino)alkylphosphonates,
phosphiteꢀphosphonate rearrangement.
Earlier, we have obtained a broad range of substiꢀ
tuted αꢀ(Nꢀacylamino)alkyl phosphites and found that
these compounds enter into the Perkow intramolecular
reaction or undergo phosphiteꢀphosphonate rearrangeꢀ
ment, depending on the nature of the chlorocarbonyl
and amido fragments; if a phosphite contains a chloro
ketone fragment, the above reactions occur concurꢀ
rently.1—3 In addition, we found that the presence of a
proton at the amide N atom is a necessary condition for
the phosphiteꢀphosphonate rearrangement to occur.4
In continuation of these investigations, we syntheꢀ
sized previously unknown αꢀ(Nꢀsulfonylamino)alkyl
phosphites and studied the possibility of analogous rearꢀ
rangements in these compounds.
Hydroxy derivatives 2 and 3 readily react with diethyl
phosphorochloridite in THF at –5 to 0 °C in the presꢀ
ence of Et3N to give phosphonates 4 and 5 (Scheme 2).
Scheme 2
Results and Discussion
The reactions of αꢀchloro aldehydes 1 with benzeneꢀ
sulfonamide (Scheme 1) were used to obtain Nꢀsulfonylꢀ
hemiaminals (2 and 3), which served as the starting comꢀ
pounds in the synthesis of the target products.
R = Cl (a), EtOC(O) (b)
Scheme 1
R = Cl (a), EtOC(O) (b)
The expected intermediate phosphites were not deꢀ
tected by 31P NMR spectroscopy; apparently, they readily
undergo phosphorotropic isomerization into Cꢀphosphoꢀ
rylated products 4 and 5.
The structures of hydroxyalkyl amides 2 and 3 and
phosphonates 4 and 5 were determined using 1H and
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 825—826, May, 2002.
1066ꢀ5285/02/5105ꢀ897 $27.00 © 2002 Plenum Publishing Corporation

898
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
Guseinov and Burangulova
31P NMR spectroscopy. Thus the 1H NMR spectra of
perature for 1 h and at ∼20 °C for 1 h. The precipitate that
formed was filtered off, the solvent was removed, and the prodꢀ
uct was precipitated with ether. The crystals that formed were
filtered off, washed with ether, and dried.
compounds 4 and 5 show a signal for the CHP proton at
2
3
δ 4.6—4.9 (dd, JPH = 20.0 Hz, JHH = 7.5—10.0 Hz).
The presence of two close signals in the 31P NMR
spectrum of compound 5 (δ 15.35 and 15.48) suggests
the formation of two diastereomers.
Diethyl 2,2,2ꢀtrichloroꢀ1ꢀ(phenylsulfonamido)ethylphosꢀ
phonate (4a). Yield 75%, m.p. 101—104 °C. Found (%):
Cl, 25.31; N, 2.95; P, 7.42. C12H17Cl3NO5PS. Calculated (%):
Cl, 25.08; N, 2.30; P, 7.30. 1H NMR (acetoneꢀd6), δ: 1.12 (t,
Hence, like αꢀ(Nꢀacylamino)ꢀ and αꢀ(Nꢀphosphorylꢀ
amino)alkyl phosphites, αꢀ(Nꢀsulfonylamino)alkyl phosꢀ
phites containing a proton at the amide N atom undergo
phosphorotropic isomerization to give phosphonates.
6 H, 2 Me); 4.03 (m, 4 H, 2 OCH2); 4.66 (dd, 1 H, CH, 2JPH
20 Hz, JHH = 10 Hz); 7.55 (m, 3 H, Ph); 7.90 (m, 3 H, Ph,
NH). 31P NMR (acetone), δ: 11.69.
=
3
Ethyl 2,2ꢀdichloroꢀ3ꢀdiethoxyphosphorylꢀ3ꢀ(phenylsulfonꢀ
amido)propionate (4b). Yield 82%, m.p. 145—147 °C. Found (%):
Cl, 15.41; N, 3.45; P, 6.75. C15H22Cl2NO7PS. Calculated (%):
Experimental
1
Cl, 15.37; N, 3.03; P, 6.71. H NMR (acetoneꢀd6), δ: 1.30 (m,
1
H NMR spectra were recorded on a Tesla BW spectromꢀ
9 H, 3 Me); 4.12 (m, 4 H, 2 OCH2); 4.37 (q, 2 H, OCH2); 4.90
2
3
eter (100 MHz) with HMDS as the internal standard. 31P NMR
spectra were recorded on a Bruker WPꢀ80 spectrometer with
85% H3PO4 as the external standard.
(dd, 1 H, CH, JPH = 20 Hz, JHH = 7.5 Hz); 5.90 (br.s, 1 H,
NH); 7.60 (m, 3 H, Ph); 8.06 (m, 2 H, Ph). 31P NMR (acꢀ
etone), δ: 14.40.
2ꢀChloroꢀ2ꢀ[phenylsulfonamido(diethoxyphosphoryl)meꢀ
thyl]butanoꢀ4ꢀlactone (5). Yield 78%, m.p. 148 °C. Found (%):
Cl, 8.75; N, 3.05; P, 7.21. C15H21ClNO7PS. Calculated (%):
Cl, 8.34; N, 3.29; P, 7.28. 1H NMR (acetoneꢀd6), δ: 1.30 (m,
6 H, 2 Me); 2.55, 3.08 (both m, 2 H, CH2); 4.05—4.79 (m,
7 H, 3 OCH2, CH); 7.55 (m, 4 H, Ph, NH); 8.00 (m, 2 H, Ph).
31P NMR (acetone), δ: 15.35, 15.48.
αꢀChloro aldehydes 1a—c were prepared according to the
known procedure.5
Nꢀ(2,2,2ꢀTrichloroꢀ1ꢀhydroxyethyl)benzenesulfonamide (2a)
was obtained as described in Ref. 6, m.p. 181 °C (cf. Ref. 6:
m.p. 181 °C). 1H NMR (acetoneꢀd6), δ: 5.40 (s, 1 H, CH);
6.50 (br.s, 1 H, NH); 7.57 (m, 3 H, Ph); 7.92 (m, 2 H, Ph).
Ethyl 2,2ꢀdichloroꢀ3ꢀhydroxyꢀ3ꢀ(phenylsulfonamido)propꢀ
ionate (2b). A mixture of aldehyde 1b (18 g, 0.096 mol) and
benzenesulfonamide (5.07 g, 0.032 mol) was heated at 90 °C
for 1 h. The excess of the aldehyde was removed and the prodꢀ
uct was precipitated with ether. The crystals that formed were
filtered off, washed with ether, and dried. The yield of comꢀ
References
1. F. I. Guseinov, R. N. Burangulova, and V. V. Moskva,
Zh. Obshch. Khim., 1997, 67, 163 [Russ. J. Gen. Chem., 1997,
67 (Engl. Transl.)].
pound 2b was 65%, m.p. 100 °C. Found (%): Cl, 20.31; N, 4.25.
1
C
11H13Cl2NO5S. Calculated (%): Cl, 20.76; N, 4.09. H NMR
2. F. I. Guseinov, R. N. Burangulova, and A. G. Kharlamova,
Abstrs., XIV Int. Conf. on Phosphorus Chemistry (Cincinnati,
Ohio, USA, July 12—17, 1998), Cincinnati, 1998, 67.
3. F. I. Guseinov, R. N. Burangulova, G. U. Klimentova, and
V. V. Moskva, Phosphorus, Sulfur and Silicon, 1999, 147, 479.
4. F. I. Guseinov, R. N. Burangulova, G. U. Klimentova, and
V. V. Moskva, Abstrs., XIV Int. Conf. on Phosphorus Chemisꢀ
try (Cincinnati, Ohio, USA, July 12—17, 1998), Cincinnati,
1998, 66.
(CDCl3), δ: 1.17 (m, 3 H, Me); 4.15 (m, 2 H, OCH2); 5.43 (d,
1 H, CH, J = 10 Hz); 6.75 (d, 1 H, NH, J = 10 Hz); 7.47 (m,
3 H, Ph); 7.85 (m, 2 H, Ph).
2ꢀChloroꢀ2ꢀ[phenylsulfonamido(hydroxy)methyl]butanoꢀ4ꢀ
lactone (3) was obtained analogously. The yield of compound 3
was 70%, m.p. 126—130 °C. Found (%): Cl, 11.41; N, 4.67.
C
11H12ClNO5S. Calculated (%): Cl, 11.62; N, 4.58. 1H NMR
(CDCl3), δ: 2.52, 3.22 (both m, 2 H, CH2); 4.55 (m, 2 H,
OCH2); 5.60 (d, 1 H, CH, J = 8.7 Hz); 6.30 (d, 1 H, NH, J =
8.7 Hz); 7.62 (m, 3 H, Ph); 7.90 (m, 3 H, Ph, OH).
The reactions of hemiaminals 2a,b and 3 with diethyl phosꢀ
phorochloridite. Triethylamine Et3N (0.05 mol) was added at
–5 °C to a stirred solution of a mixture of hemiaminal 2a,b or 3
(0.05 mol) and diethyl phosphorochloridite (0.05 mol) in 50 mL
of anhydrous THF. The reaction mixture was kept at this temꢀ
5. F. I. Guseinov and V. V. Moskva, Zh. Org. Khim., 1994, 30,
360 [Russ. J. Org. Chem., 1994, 30 (Engl. Transl.)].
6. J. F. Lichtenberger, J. Chem. Soc. Fr., 1955, 669.
Received June 20, 2001;
in revised form February 13, 2002