REARRANGEI~NT OF S-2-HYDROXYALKYL ESTERS OF DIBUTYLTHIOPHOSPHORIC ACIDS

O. N. Nuretdinova and F. F. Guseva UDC 542.952.1 : 547.1'118

Based on the assumption that the rearrangement of the S-2-hydroxyalkyl esters of phosphorus acids proceeds via closure of the thiaoxaphospholane ring [i], we synthesized some S-2-hydroxyalkyl esters of di-tert-butyl thiophosphoric acid (BTPA), which, in our opinion, should not isomerize to the 2-mercaptoalkyl esters in view of the steric hindrance in the step of closing in the intermediate thiaoxaphospholane ring.

BTPA was obtained from the corresponding ammonium salt by treatment with'HCl. In contrast to [2] (5~P --25 ppm), the BTPA obtained by us has ~3~p --44 ppm, and decomposes when heated, distilled, or stored (% 20~ Consequently, after removal of the solvent and determination of the constants, the undistilled acid was used immediately in the reactions with alkene oxides. To compare the reactivity of the BTPA and the ability of its S-2-hydroxy- alkyl esters to rearrange to the 2-mercaptoalkyl esters we ran the analogous reactions of the alkene oxides with di-n-butylthiophosphoric acid. It turned out that BTPA reacts more rapidly and vigorously with the alkene oxides. The S-2-hydroxyalkyl esters of dibutylthio- phosphoric acids are formed in both cases, which differ in the ability to rearrange. Whereas the S-2-hydroxyalkyl esters of di-n-butylthiophosphoric acid are converted to the 0-2- mercaptoalkyl esters even during preparakion, the S-2-hydroxyalkyl esters of BTPA remain un- changed under these conditions (one signal in the sip NMR spectrum at --16 to --18 ppm, and the absorption band of the OH group at 3400 cm -~ in the IR spectrum).

(t-C4HgOhPSOH + R t - - C H - - C H - - R 2 -~ (t-C~H~O)~PSCHCHOH

0 0 R1R 2 RI----H, R ~ = C H a (I); R1----R~=CHa(II)

(n-C.HgO)zPSOH + RI--CH--CH--R2-o (T~-CIHgO)2PSCHCHOH -. (n-C,HgO)~POCHCHSH \ / N I I II r I

0 0 R ~ It ~ 0 R z R~

R'=H, R2=CHa (III); B1=R2=CHa (IV)

When stored, the S-2-hydroxyalkyl esters of di-n-butylthioPhosphric acid are converted completely to the O-2-mercaptoalkyl esters (III) and (IV) (absent are the absorption of the O11 group in the IR spectrum and the signal at --26 to --28 ppm in the 3~p N~4R spectrum, which signal is characteristic for the S-2-hydroxyalkyl esters of this series, and present are the absorption band, characteristic for the SH group, in the IR spectrum and only one signal, with ~Ip +2 ppm, in the 31p NMR spectrum). In contrast to the S-2-hydroxyalkyl esters of di-n-butylthiophosphoric acid, the rearrangement of esters (I) and (II) is also not observed" when they are stored under nitrogen in a sealed ampul for a month~ Esters (I) and (II) decompose (based on the elemental analysis results) in an open ampul with the evolution of isobutylene.

As a result, O,O-dialkyl S-(2-hydroxyalkyl) thiophosphates, whichcontain twosterically hindered alkoxy groups on the phosphorus atom, lose the ability to rearrange to the 2-mercapto- alkyl esters. When heated to 130-135 ~ , thiophosphate (I) decomposes with the evolution of gaseous products. The main signal in the sip NMR spectrum of the viscous residue in the distillation flask lies in the region of the standard and probably corresponds to HaPO~.

EXPERImeNTAL

The ~ip NMR spectra were taken on a YaMR-KGU-4 NMRspectrometer at a frequency of 10.2~z, and using 85% H3PO~ as tile standard.

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch of the Academy of Sciences of the USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1901-1903, August, 1979. Original article submitted February 13, 1979.

0568-5230/79/2808-1765507.50 �9 1980 Plenum Publishing Corporation 1765

Di-tert-butylthiophosphoric Acid (BTPA). With cooling (~ i0~ to a solution of 3.79 g of the ammonium salt of BTPA in 50 ml of dry ether was added 12.3 ml of an ethersolution that contained 0.56 g of HCI. After separating the precipitated NH4CI the ether was removed in vacuo, first at i0 mm, and then at 0.2 mm. We obtained 2.93 g (80%) of BTPA; d42~ 1.0622; n~ ~ 1.4632. Found, %: P 13.78. CaHIgO3PS. Calculated, %: P 13.71. ~31p 44 ppm.

O,O-Di-tert-butyl S-(2-Hydroxyalkyl) Thiophosphates (I) and ~II). To a solution of 2.5 g of BTPA in 50 ml of dry ether was added a threefold excess of propylene oxide, after which the mixture was refluxed for 30 min and then evaporated in vacuo at i0 and 0.2 mm to give (I); d~ ~ 1.0720; n~ ~ 1.4670. Found, %: C 46.80; H 9.16; P 10.95. C~IH2504PS. Calculated, %: C 46.48; H 8.80; P 10.90. ~ a~p --18 ppm. In a similar manner we obtained (II) in quan-

n 2o titative yield; d~ ~ 1.0675; ~ 1.4662. Found, %: C 48.37; H 9.00; P 10.34; S 10.75. C~H2~O~PS. Calculated, %: C 48.32; H 9.06; P 10.40; S 10.73. ~ a~p --18 ppm.

O-O-Di-n-butyl 0-(2-Mercaptoalkyl) Phosphates (III) and (IV). The reactions with di- n-butylthiophosphoric acid were run the same as the preceding, with the difference that the mixture was heated for 6-8 h at ether reflux until the signal of the starting acid at -60 to --66 ppm disappeared in the alp NMR spectrum. We obtained: O,O-di-n-butyl O-(l-methyl-2- mercaptoethyl) phosphate (III); d~ ~ 1.0622; n~ ~ 1.4512. Found, %: C 46.46; H 8.79; P 10.82. C11H2sO4PS. Calculated, %: C 46.48; H 8.80; P 10.90. ~aip +2 ppm; O-O-di-n-butyl O-(l- methyl-2-mercaptopropyl) phosphate (IV); d~ ~ 1.0543; n~ q 1.4525. Found, %: C 48.35; H 9.06; P 10.50. C12H2704PS. Calculated, %: C 48.32; H 9.06; P 10.40. ~31p +2 ppm.

CONCLUSIONS

Replacing the n-butyl radical in the alkoxyl group of the S-2-hydroxyalkyl esters of dibutylthiophosphoric acid by the tert-butyl group leads to a loss in the ability to be converted to mercaptoalkyl phosphates, which is probably related to the difficulty of forming the intermediate compounds with a thiaoxaphospholane ring.

l.

2.

LITERATURE CITED

O. N. Nuretdinova and F. F. Guseva, Izv. Akad. Nauk SSSR, Ser. Khim., 1978, 2142. V. Mark and J. R. Van Wazer, J. Org. Chem., 29, 1006 (1964).

TELOMERIZATION OF 2-CHLOROPROPENE WITH CARBON TETRACHLORIDE

R. Kh. Freidlina, E. Ts. Chukovskaya, UDC 66.095.2 : 547.322 : 547.412.133 and A. A. Kamyshova

In the presence of peroxide and coordination initiators, CC14 reacts with many olefins and chloroolefins [i]. However, its reaction with 2-chloropropene has not been described. This reaction has interest as a path for the synthesis of highly chlorinated compounds that contain the CCIa and CC12 groups in the same molecule. Of the radical reactions involving 2-chloropropene, only its telomerization with l,l,l-trichloroethane has been described [2].

We studied the reaction of CCI~ with 2-chloropropene in the presence of benzoyl peroxide as well as under tile influence of coordination initiators (CI). The reaction proceeds by the scheme

CCI4 C I'" CCls

CCI s ~ CHs=CCICHa ~Ctl~ CCIs(CH~CCI)nCI(Tn) I CH3

n = l , 2

where CI = Fe(CO) 5 + i-PrOH; Fe(CO) 5 + EtOH.

The reaction was run with a ratio CCI~ : C3H5CI = 2 in order to shift the process in the direction of the predominant formation of TI. The yields of the telomers were: 44-52 for TI,

Institute of Heteroorganic Compounds, Academyof Sciences of the USSR, Moscow. Trans- lated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1903-1905, August, 1979. Original article submitted February 12, 1979.

1766 0568-5230/79/2808-1766507.50 �9 1980 Plenum Publishing Corporation