Bull. SOC. Chin. Belg. vol.90/nD 1/1981 SHORT COM!IUNICATION

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS X X X I X . '

THE REACTION OF 8-PROPIOLACTONES WITH 2,4-BIS(4-HETHOXYPHENYL)- 1,3,2,4-DITHIADIPHOSPHETANE 2,4-DISULFIDE

R . SHABANA,a J. B. RASMUSSEN AND S.-0. LAWESSON

Department of Organic Chemistry, Chemical Institute, University of Aarhus. DK-8000 Aarhue C, Denmark

Received 12/1/81 - Accepted 22/1/81

It is well known that 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphos- phetane 2,4-disulfide, 1, is a most effective thiation reagent for ketones." carboxamides ,'-' esters,' 1 ' ' - S-subst itu ted thloesters,e enaminones , I ' lac- tams," and Y- and 6-lactones."

In our attempts to transform @-propiolactone'' &, and 3-methyl-8-pro- piolactone" s, into the corresponding thionolactones with compound 1, the ring system 2 was formed instead. This is analogous to the formation of a P-heterocycle by reacting a diaziridinone" with 1. The structure of 1 was

established by microanalyses, MS, IR, 'H-, I3C- and 31P-NMR.

R

a t R = H 1 - Qo A Rqr&ocH3 - bt R = CHI

0

2 - 1

In the "P NUR spectra, 2 abaorbs at 6 82.87 while 2 shows resonance8 at 6 80.45 and 79.97. in accordance with data from the literature." The C(4) resonance of 2 shows a doublet at 6 191.6 (d';c = 4.0 Hz), whereas 2, which contain. two chiral centres, exhibits two doublets at 6 191.4 (J& = 4.0 Hz) and 6 190.4 ( J i c I 2 . 9 He). The isomers could not be separated. These data""*" ruggent that acyl-oxygen flsaion" of 2 has occurredyleld-

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ing the ring system 2. Attempts to rearrange" 2 at elevated temperature or to thiate 2 with 1 w e r e unsuccessful.

EXPERIMENTAL

'H, "C, and ,'P NMR. IR and mass spectra w e r e obtained as earlier de- scribed.'*'' Coupling constants are given as l - ' l . Microanalyses were carried out by Novo Microanalytical Laboratory, Novo Industri A/S. Novo All&, DK-2880 Bagsverd, supervised by Dr. R . E. Amsler. Silica gel 60 (Merck) was used for column chromatography. M.p.'s are uncorrected. The compounds 1, &, and are commercially available.

(0.02 mole of 2a and 4.04 g of 1 w e r e refluxed in 25 ml anhydrous toluene with stirrlng until a had been ronsumed (tlc). The solvent was evaporated under reduced pressure and the residue was extracted several times withether. The combined ether extracts were concentrated, whereby a precipitated di- rectly. Yield 60%. M.p. 10GL. 'H NMR (CDCl,): b 3.0-7.2fZH. m ) ; 7.9 (3H. s)# 4.1-5.4 (2H. m ) ; 6.9 (ZH, dd, JPH = 4 Hz, GHH = 9 Hz)# 7.9 (2H. dd. Jp = 15 Hz, .'HH = 9 Hz). "C NMR (CDCl,): 6 191.6 (d, d'ep = 4.0 Hz); 163.7 rd, J l p = 3.5 Hz); 13'3.8 (d, u'ep = 14.8 Hz); 125.5 (d. u'bp = 137.5 Hz); 114.1 (d,

;i;e TM+, 97). 246 (47). 202 (60). 187 (42), 139 (100). IR (CHCl,): 1690 cm-' ('2x0). Analyses C, H. p.

When the residue was purified by column chromatography (eluent 1 1 1 CHaCl./light petroleum) 2,4,6-tris(t~-methoxyphenyl)-l,3,5,2,4,6-trioxatri- phosphorinane-2,4,6-trisulfide," was isolated in 2% yield.

2(~-Methoxyphenyl)-6-methyl-l,3~2-oxathiaphosphorinan-~-one 2-sulfide, 2. The reaction conditions are as for 2. Compound 2 could not be recrys- tallized directly, but was purified by column chromatography (CH,Cl. as e- luent). Yield 53%. M.p. 74-75%. 'H NMR (CDCl,): 6 1.5 (3H, d, J = 6 Hz)# 2.9-7.0 (2H. m ) ; 3.8 (3H, a); 4.8-5.5 (1H. m); 6.9 (2H. dd, 2 p ~ = 4 Hz, Y'HH= 9 Hz); 7.9 (2H. dd, JPH = 15 Hz. UHH = 9 Hz). "C NMR (CDC1,): 6 191.4 d c = 4 Hz)*, 190.4 (d, J f & = 5.6 H Z ) ~ 177.6 (d, Jjc== 14.7 Hz)*. 172.5 (d, J$c = 14.9 Hz); 124.5 (d J b 130.6 Hz)*, 125.5 ( d , .'bc = 118.1 Hz); 117.6 (d, ~ ? $ r = 17.0 Hz *. 115.8 (id: u $ c = 1h.O Hz); 69.8 (d, U& = 5;6 Hz)* 55.2 (a)*, 55.2 ( 9 ) ; 48.1 ( 5 ) " . 47.6 (d. .pc = 3 . 6 Hz); 21.7+d.=u$c = 10.6 Hz)'. 22.0 (d,

2(~-Methox~phenyl~-l.3.2-oxathia~hosphorinan-~-one 2-sulfide, 2. 1.44 g

17.1 Hz)# 62.0 (d. JEP = 6.1 Hz); 55.5; 42.0. US: m/e (% rel. int.):

d, 2.9 Hz); 167.2 (d, ubc = 3.5 Hz)*. 162.8 [d.

8.6 Hzl, 74.1 (d.v

= 8.1 Hz . Ths. values marked corresponQ to the most abundant i s o m e ~ ~ r a t i o 1 0 1 1 . MS: m/e (4: rel. int.): 288 (M , 67). 272 (12 260 (24). 202 (71). 187 (37 I , 179 (80). 69 (100). IR (CHCl,): 1690~m'~(C=O Acknowled ement - Thanks are expressed to DANIDA for a fellowship to one of us 1.3!2,1-dithiadiphosphetane 2.4-disulfide.

REFERENCES

RS afd to Fluka AC for a generous supply of Z.b-bis(4-methoxyphenyl)-

1. 2. 3.

4. 5. 6.

7.

8 .

9.

10. 1 1 .

12.

13. 14.

15.

16.

Part XXXVIII. S.Scheibye, S.-0.Lawesson and C.Remming (submitted). On leave from the National Research Centre. Dokki. Cairo. Egypt. B.S.Pedersen, S.Scheibye, N.H.Nilsson and S.-0.Lavesson. Bull.Soc.Chim. Belg. a, 223 (1978). S.Scheibye. B.S.Pedersen and S.-O.Lawesson, Bull.Soc.Chim.Belg.8J,299(1978 l? S.Scheibye. B.S.Pedersen and S.-O.Lawesson, Bull.Soc.Chim.Belg. g, 229(197 H.Fritz, P.Hug, S.-O.Lawesson, E.Logemann, B.S.Pedersen, H.Sauter, S . Scheibye, and T.Uinkler, Bull.Soc.Chim.Belg. a, 525 (1978). K.Clausen, B.S.Pedersen, S.Scheibye, S.-0.Lawesson and J.H.Bowie, Int. J. Mass Spectrom.Ion Phys. a, 227 (1979). K.Clausen. B.S.Pedersen. S.Scheibye. S.-0.Lawesson and J.H.Bowie, Org. Mass Spectrometry lb, 1 0 1 (1979). B.S.Pedersen. S.Scheibye. K.Clausen and S.-O.Lawesson, Bull.Soc.Chim. Belg. Q, 293 (1978). B.S.Pedersen and S.-O.Lawesson, Tetrahedron 2. 2433 (1979). R.Shabana, J.B.Rasmussen. S.O.Olesen and S.-0.Lawesson. Tetrahedron s, 3047 (1980). R.Shabana, S.Scheibye, K.Clausen. S.O.Olesen and S.-0.Lawesson. Nouv. J. Chim. 4, 47 (1980). S.ScheTbye, J.Kristensen and S.-O.Lawesson, Tetrahedron 2, 1339 (1979). Y.Etienne and N.Fischer, Heterocyclic Compounds Part 11, Chapter VI, 729-859. ed. A.Weissberger, Interscience Publ., 1964. C.L'abb6. J.Fl6mal. J.-P.Declercq. C.Cemain and M.van Meerssche. Bull. Soc.Chim.Belg. E, 737 (1979). H.J.Meyer and S.-0.Lawesson (in manuscript).

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