FR2714060A1 - Diphosphine dioxides useful for the extraction of actinides and phosphonium disks for their preparation. - Google Patents

Abstract

The invention relates to diphosphine dioxides, which can be used for the extraction of actinides such as Pu, Am, Np from aqueous effluents and from concentrates of fission products from plants for the reprocessing of spent nuclear fuel. These diphosphine dioxides correspond to one of the following formulas: (CF DRAWING IN BOPI) in which R1, R2, R3, R4, R and R 'are optionally substituted alkyl or aryl groups, and Q and Q' are chains hydrocarbons optionally comprising oxygen, sulfur or nitrogen atoms.

Description

DIOXIDES OF DIPHOSPHINES USEFUL FOR THE EXTRACTION OF

  ACTINIDES AND PHOSPHONIUM DISELS FOR THEIR PREPARATION

  The subject of the present invention is dioxides of diphosphines which can be used in particular for the extraction of actinides. More specifically, it relates to diphosphine dioxides for selectively extracting actinides from high-salinity aqueous effluents, fission product concentrates and solutions 10 from fuel reprocessing plants.

nuclear uses.

  It is known that poly (heteroatomic) macrocyclic compounds constitute a very interesting class of ligands because they possess complexation properties with respect to transition metals. Among these macrocyclic compounds, stable P-C bonded compounds should have novel properties in complexation. Also, work has been done to synthesize such compounds, particularly in the form of polyoxygenated diphosphorus macrocycles, as described by Cristau et al in New Journal of Chemistry, Vol. 8, No. 3, 1984, p. 191-199, and by Christol et al in Tetrahedron Letters n. 28, 1979, p. 2591-2594. Other macrocyclic diphosphines are also described by Chan et al.

  in J. Org. Chem., Vol. 39, No. 12, 1974, p. 1748-1752.

  Polyoxygenated or polysulfurized diphosphorus macrocyclic compounds are further described by Markl et al.

  in Tetrahedron Letters, Vol 33, No. 25, 1992, p. 3621-

  3624 or by Bader and Lindner, Coord. Chem. Rev., 1991,

108, p. 27.

  However, none of these authors has considered using such macrocyclic compounds for

the extraction of actinides.

  The present invention specifically relates to new diphosphine dioxides which are particularly suitable for the extraction of actinides from aqueous effluents, generally acid, high salinity and fission product concentrates from the reprocessing plants.

used nuclear fuels.

  According to the invention, the dioxides of diphosphines correspond to one of the following formulas: RP c R3 R2 / f \ R4

/

R-P = O O = P-R '(II)

  Wherein: R1, R2, R3 and R4, which may be the same or different, represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from carboxy, alkoxy groups; hydroxy and amino; and aryl groups unsubstituted or substituted by at least one group selected from alkyl, carboxy, alkoxy, hydroxy and amino groups; - R and R 'which may be the same or different represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from carboxy, alkoxy, hydroxy and amino; aryl groups which are unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; Q and Q ', which may be identical or different, represent a group of formula:

- (CH2) 1-,

  - (CH2) m -CH = CH- (CH2) n-, (CH2) mCC- (cH2) n-, - (CH2) p- [O- (CH2) q] r-, (CH2) p- [ S- (CH2) q] r-, - (CH2) p- [O-R5-O- (cH2) q] r-, or

- (CH2) p- [N (R6) - (CH2) q] r-

  wherein R5 is phenylene or a bivalent group derived from a heterocyclic ring, R6 is H or alkyl and 1, m, n, p, q and r are integers such that 3 <1 <16 3 < q <16 1 <m <16 1 <r <16 1 <n <16 3 <p <16 provided that

  1) in formula I, Q does not represent - (CH2) 3-

  O- (CH2) 3- or (CH2) 3-O- (- O- (CH2) 3- when R1, R2, R3 and R4 are all phenyl, or (CH2) 1 when R1, R2, R3 and R4 are all phenyl or benzyl, 2) in formula II, Q and Q 'do not both represent (CH2) 3-O- (CH2) 3- or (CH2) 3-O- (CH2) 3 when R and R 'are both phenyl, and 3) in formula II, Q and Q' do not represent - (CH2) 1- when R and R 'are both

phenyl or benzyl groups.

  The phosphine oxides described above are particularly interesting because they make it possible to extract more than 90% of the plutonium present in

  very low concentrations in aqueous effluents.

  They therefore have performances equivalent to

  those of the CMPO (octyl (phenyl) -N, N'-diiso-

  butylcarbamoylmethylphosphine) which is the product

  currently used for this extraction.

  In the formulas given above, the alkyl groups which may be used for R 1, R 2, R 3, R 4, R 6, R and R 'may be linear or branched groups, generally having from 1 to 16 carbon atoms.

  carbon, and preferably from 4 to 12 carbon atoms.

  These alkyl groups may be substituted by one or more groups selected from alkoxy, carboxy, hydroxy and amino groups, the alkoxy groups having

  generally from 1 to 12 carbon atoms.

  The aryl groups which may be used for R 1, R 2, R 3, R 4, R and R 'may comprise one. or more aromatic rings, and optionally substituted with one or more groups selected from alkyl, alkoxy, carboxy, hydroxy and amino groups

such as those described above.

  By way of example of aryl groups which may be used, mention may be made of phenyl groups and

benzyl.

  For R6, the phenylene group may be 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; when R6 is a group derived from a heteroatomic ring, this ring may be, for example, furan, thiophene,

  quinoline, pyridine and their derivatives.

  When R 6 is derived from a heteroatomic ring, a ring derived from pyridine, for example the pyridine diyl group of formula X, is preferably used. In formulas (I) and (II) given above, Q and Q 'may various hydrocarbon chains optionally comprising a double or triple bond, one or more oxygen and / or sulfur atoms, and

aromatic nuclei.

  Preferably, Q e: / or Q 'comprise oxygen atoms and for example correspond to the following formulas: - (CH 2) 3 -O- (CH 2) 3 and

- (CH2) 3- - (CH2) 2-

  The diphosphine dioxides of formula (I) can be prepared by a conventional method from the corresponding phosphonium disks, by subjecting the corresponding phosphonium disalt of formula:

R1 / R3

R2- - p-Q-uP-R4, 2XG (III)

R7 / - \ R8

R

  wherein R 1, R 2, R 3, R 4 and Q have the meanings given above, R 7 and R 8 are benzyl or phenyl and X is a halogen atom. The diphosphine dioxides of formula (II) can also be prepared by a conventional process from the corresponding phosphonium disks, by subjecting the corresponding phosphonium disalt of the following formula to basic hydrolysis: ## EQU1 ##

PG PG (IV)

2XQ

Q R8

  wherein R, R ', Q and Q' have the meanings given above, R7 and R8 are benzyl groups or

  phenyl, and X is a halogen atom.

  The invention also relates to the phosphonium disks of formulas (III) and (IV) given above. In these phosphonium disks, X

  is preferably a bromine atom or an iodine atom.

  The phosphonium disks of formula (III) can be prepared from the dihalides of formula QX2 by reaction thereof with the corresponding phosphines of formula PR1R2R7 and PR3R4R8 as described by Cristau et al, in the New Journal of Chemistry, 8, No. 3, 1984, p. 192. These disks of formula (III) can also be prepared by reaction of the diphosphines of formula PR1R7-Q-pR3R8 with the

R2X and R4X alkyl halides.

  The phosphonium disks of formula (IV) can be prepared by the method described by Cristau et al in the New Journal of Chemistry, Vol 8, No. 3, 1984, p. 191 to 199, by coupling between a biphosphine of

  RR7P-Q-PR'R8 formula with a dihalogenated derivative Q'X2.

  The subject of the invention is also a process for separating actinides present in an aqueous solution resulting from the reprocessing of spent nuclear fuels, which consists in bringing this solution into contact with an immiscible phase comprising at least one diphosphine dioxide corresponding to one following formulas: Q Rl OO R3

PR2 / R R-P = O

R2 / () \ R4

  wherein: - R1, R2, R3 and R4, which may be the same or different, represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from alkoxy, carboxy, hydroxy and amino; and aryl groups unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; - R and R 'which may be the same or different represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from alkoxy, carboxy, hydroxy and amino groups; aryl groups which are unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; Q and Q ', which may be identical or different, represent a group of formula:

- (CH2) 1-,

  - (CH2) m -CH = CH- (CH2) n-, - (CH2) p-CC- (CH2) n-, - (CH2) p- [O- (CH2) q] r-, - (CH2) p- [S- (CH2) q] r-, - (CH2) p- [O-R5-O- (CH2) q] r-, or

- (CH2) p- [N (R6) - (CH2) q] r-

  wherein R5 is phenylene or a divalent group derived from a heterocyclic ring, R6 is H or alkyl and 1, m, n, p, q and r are integers such that 3 <i <16 3 Cq <16 1 <m <16 1 <n <16 1 <r <16 3 <p <16

  to extract the actinides in the immiscible phase.

  According to a first embodiment of the process of the invention, the immiscible phase is an organic liquid phase constituted by an organic solvent

  containing in solution the phosphine oxide (s).

  The organic solvents which may be used are in particular ethers and alcohols: The ethers may be nitrophenylalkylethers such as nitrophenylhexyl ether and nitrophenyloctyl ether. As an example of alcohol

  usable, mention may be made of isotridecanol.

  The concentration of phosphine oxide in the organic phase is chosen so as to obtain the best extraction rate without formation of precipitate or a third phase. It depends in particular on the solubility of the phosphine oxide in the organic solvent used. Generally, we use a

  phosphine oxide concentration of 10-3 to 0.2 mol / l.

  The aqueous solutions containing actinides which can be treated by this process are, in particular, acidic aqueous solutions, for example solutions of nitric acid or hydrochloric acid, preferably nitric solutions having a nitric acid concentration of 10-7. 1 to 4 mol / l, which may also contain sodium in relatively high concentration, for example about 4 mol / l of Na + The actinides present in these solutions (aqueous effluents or fission product concentrates) are for example Pu, Np, Am to

  concentrations generally below lg / l.

  According to the invention, the bringing into contact between the aqueous solution and the immiscible organic phase can be carried out in conventional apparatus

  of liquid-liquid extraction such as mixers-

  decanters, exchange columns, pulsed columns, etc. Generally, we operate at atmospheric pressure

and at room temperature.

  After separation of the actinides in the immiscible phase, these can be recovered by bringing it into contact with an aqueous solution of

  stripping having a pH ranging from 1 to 7.

  Generally, the aqueous reextract solution is an aqueous solution of organic acid or organic acid salt such as oxalic acid, citric acid, oxalates and citrates. The use of such solutions makes it possible to obtain reextraction with

high yields.

  According to a second embodiment of the process of the invention, the immiscible phase consists of a liquid membrane comprising the phosphine oxide (s), one of the faces of the membrane being in contact with each other. contact with the aqueous solution containing the actinides and the other side being in contact with an aqueous stripping solution such as those described above. The liquid membrane may be, for example, a supported liquid membrane constituted by a microporous membrane acting as a support, the pores of which are filled with diphosphine oxide (s) dissolved in an organic solvent which is immiscible with water.

  such as the ethers and alcohols mentioned above.

  This microporous membrane may be made of polypropylene, polyvinylidene fluoride or polytetrafluoroethylene, and may serve as a separation between a first compartment in which the aqueous solution to be treated is located and a second compartment in which the aqueous solution is located.

reextraction.

  To obtain a good extraction with the supported liquid membranes, it is advantageous to use membranes having a small thickness, a high porosity and a small pore diameter. These membranes can be used in the form of modules such as ultra or microfiltration modules with flat membranes or hollow fibers, which make it possible to treat high flow rates of fluid. With such membranes, the aqueous reextraction solution can be constituted as previously by a solution of citric acid, oxalic acid or

a salt of these acids.

  Other features and advantages of the invention will appear better on reading the following examples given of course by way of illustration and not limitation, with reference to the appended figure. The attached figure shows schematically an actinide extraction device using a

liquid membrane supported.

  Example 1 Preparation of 4-oxa-1,7-dioxide

  heptamethylene bis dodecylphenylphosphine (compound n 1) of formula:

O O

IIA zA \ Nl Xi i 0 php vO- vPPh

I I

C2H5

C44H7203P2 M = 686.99 CH

C44H7203P2; M = 686.99

  a) Preparation of 4-oxa-1,7-dibromide

  heptamethylene bis dodecyldiphenylphosphonium (compound n0 2) of formula: Ph, / O / Ph 2 Br

-I I

C-H, C12MH25

  C54H82Br2OP2; M = 969.02 This preparation corresponds to the following reaction scheme: ## STR2 ## It is carried out under a pure nitrogen atmosphere and

dry.

  In a 250 ml bicol with a condenser, 10.7 ml (45 mmol) of 1-bromododecane and 7.0 g (14.88 mmol) of 4-oxa-1,7-heptamethylene bis diphenylphosphine are introduced into 80 ml of anhydrous dimethylformamide. We bring to 150 C for 20h. It is precipitated in ether and 13.80 g of white gum (14.24 mmol), which does not recrystallize in CHCl3 / ethyl acetate (AcOEt), are obtained (after drying under 0.1 mmHg / P2O5 / 4h). Ion exchange was carried out using 1.10 g (1.13 mmol) of gum and 1.46 g of NaBPh4. 1.60 g (1.1 mmol) of white powder (after drying under

p = 0.1 mmHg / t = 80 C / P 2 O 5 / 24h).

  The yield is 96%. Identification F = 270 ° C (di-traphenylborated salt) 31 P NMR of the dibromated salt (200 MHz, CDCl 3) 626.64 (s) IR (KBr of the trittenylborated salt) 465 ff-480 ff-605 F-615 m-625 ff-705 FF 740

  F - 745 GB - 845 e - 1035 e - 1065 e - 1140 e - 1150 e

  1180 ff - 1220 ff - 1265 ff - 1315ff - 1360 f - 1380 E -

  1420 F - 1475 F - 1580 m - 1670 m - 3000 m - 3060 m.

  b) Preparation of 4-oxa-1,7-dioxide

  heptamethylene bis dodecylphenylphosphine.

  This preparation corresponds to the following reaction scheme: NaOH OO Ph2p PP2 2 oC Plane Benzene-H-2O 11H, 5 12H25 6h71C 12H25 12H25 (Compound No. 2) (Compound No. 1) In a 250ml bicol equipped with a refrigerant, it is introduced 5.2 g (130 mmol) of NaOH in 25 ml of water,

  12.16 g (12.54 mmol) of 4-oxa-1,7-dibromide

  heptamethylene bis dodecyldiphenylphosphonium (compound n 2) obtained above and 80 ml of benzene. Refluxed (71 C) for 16h then decanted and extracted with chloroform; the organic phases are combined, washed with water, dried over Na 2 SO 4 and the solvent is then removed on a rotary evaporator. We get a white solid that i'on

  recrystallized from benzene / hexane.

  5.40 g (7.86 mmol) of white powder is obtained

  (After drying under p = 0.4 mmHg / P205 / t = 40 C / 24h).

  The yield is 63%. White solid identification

Mp 70 ° C (benzene / hexane).

  NMRH (200 MHz, CDCl 3, C = 0.08 M) δ 0.87 (t, 6H, 2 CH 3, J = 6 Hz); 1.21 (s, 36 H, 18 internal CH2); 1.45 - 2.1 (m; 16 H; 4 CH2-P = 0 and 4 internal CH2); 3.2 - 3.4 (m; 4H; 2 CH 2 -O); 7.64

  (s, 6H, meta and para); 7.6 -7.8 (m; 4H; orthor.

  31 P NMR (81 MHz, CDCl 3, C = 0.08 M) 6 41.15 (s) IR (KBr) 425 f - 455 f 480 ff - 490 ff - 505 ff - 545 F - 672 f - 695 F - 720 m - 745 F - 770 m 780 m - 845 f - 880 ff - 930 ff - 980 ff - 1000 ff - 1017 ff - 1030 f - 1075 m - 1120 FF - 1170 FF - 1190 m - 1210 m - 1315 ff - 1405 f - 1435 F - 1450 e - 1470 E - 1480 e - 1590 ff - 1900

  ff - 1970 ff - 2800 f - 2850 FF - 2920 FF - 3060 f.

Centesimal analysis

C H O

  Calculated 73.43 10.56 6.99 Found 73.10 9.57 6.97 Mass: FAB (matrix used: 1-nitrobenzyl alcohol (NOBA)

(M + 2H) + = 688.

  Example 2 Preparation of 1,8-octamethylene bis dodecylphenylphosphine dioxide (Compound No. 3) of Formula

) + (CH2) 8)

C44H7602P2; M = 699.04

  a) Preparation of 1,8-octamethylene bisdodecyldiphenylphosphonium diiodide (compound 4) of the formula:

+ 2 2+

Ph ,, H -I C t oo SI

1 C1-H5

C 12H25

C56H8612P2; M = 1075.065

  This preparation corresponds to the following reaction scheme: a. DMF / N 2 + 1: 2P / V'N 2 + 2 C 12 H 25 Br 8h; 21P0. 2H25 'b. Nal i 12H25 (Compound No. 4) It is carried out under a pure nitrogen atmosphere and dry. In a bicol of 100 ml equipped with a condenser, 0.75 ml (3.11 mmol) of 1-bromododecane and 0.5 g (1.03 mmol) of 1,8-octamethylene bis diphenylphosphine are introduced into 50 ml of anhydrous dimethylformamide. We bring to

 C for 80h.

  Ion exchange is carried out by washing

  successive with an aqueous solution of 12 mmol of NaI.

  The mixture is precipitated in ether and (after drying under p = 0.2 mm H / t = 50 C / P 2 O 5 / 24h) 0.784 g of

pale yellow solid.

The yield is 77%.

  Identification of C56H86I2P2 Pale yellow solid

F = 112 C

  1H NMR (250 MHz, CDCl 3, C = 0.3M) δ 0.74 (t, 6H, 2 CH 3, J = 7 Hz); 0.95 - 1, 25 (m; 36 H; 18 internal CH2); 1.40 (s, 16 H, 8 internal CH2); 3.1 (s, 8H, 4 CH 2 -P +); 7.5 - 7.7 (m; 12H; meta)

and para); 7.7-7.9 (m, 8H, ortho).

  31 P NMR (81 MHz, CDCl 3, C = 0.3 M) δ 28.37 (s) IR (KBr)

  455 m - 600 m - 690 F - 710 m - 735 F - 765 F - 805 f -

  845 ff - 860 ff - 890 ff - 930 ff - 1000 m - 1030 ff -

  1070 ff - 1090 f - 1120 F - 1160 m - 1180 ff - 1225 ff - 1240 ff - 1320 ff - 1340 ff - 1380 ff - 1400 m - 1435 F - 1460 m - 1485 m - 1590 m - 1820 ff - 1905 ff - 2800

  f - 2860 GB - 2930 GB - 3010 e - 3060 e.

  (b) Preparation of 1,8-octamethylene bis dioxide

dodecyl phenylphosphine.

  This preparation corresponds to the following reaction scheme:

0

+ O

  Ph.sub.2 H.sub.2 H.sub.2 O.sub.2 H.sub.2 O.sub.2 H.sub.2 O.sub.2 H.sub.2 (compound n.sub.4) (compound n12H253) (Compound No. 4) (Compound No. 3) In a bicol of C100 ml provided with 0.22 g (5.6 g) of NaOH in 4 ml of water, 0.6037 g ((0.562 mmol) of 1,8-octamethylene bis dodecyl diphenylphosphonium diiodide (compound n 4) obtained above and 50 ml of benzene is refluxed (75 ° C.) for 120 h then diluted with water, decanted and extracted with chloroform, the organic phases are combined, washed with water, dried over Na 2 SO 4 and then the solvent is removed on a rotary evaporator (after drying under p = 1 mm)

  Hg / P205 / 24h) 0.3923g of white solid.

The yield is 100%.

White solid identification

F = 57 C

  1 H NMR (250 MHz, CDCl 3, C = 0.08M) δ 0.86 (t, 6H, 2 CH 3, J = 6.8 Hz); 1.1 1.4 and 1.4 - 1.7 (m; 52 H; 26 internal CH2); 1.7 - 2.0 (m; 8H; 4 CH 2 -P = O); 7.4 - 7.5 (m, 6H, meta and para);

7.5 - 7.8 (m, 4H, ortho).

  31 P NMR (80 MHz, CDCl 3, C = 0.08 M) 6 41.2 (s) IR (KBr) 420 ff - 470 ff - 510 ff - 550 f - 675 f - 695 F - 720

  m - 742 F - 765 f - 780 f - 810 ff - 830 ff - 880 ff -

  920 ff - 930 ff - 1000 ff - 1030 ff - 1070 f - 1115 GB

  1167 FF - 1305 ff - 1375 ff - 1407 f - 1435 GB - 1465 GB

  - 1590 ff - 1820 ff - 1900 ff - 1960 ff - 2860 FF -

2920 FF - 3060 ff - 3080 ff.

  Centesimal analysis (dried 6h / P205 / 0.4 mm Hg)

C H O

  Calculated 75.60 10.96 4.58 Found 75.58 11.57 5.19 Mass: FAB (matrix used; NOBA)

(M + H) + = 699.

  Example 3 Preparation of 1,4-bis (3-dioxide

  dodecylphenylphosphinopropoxy) benzene (compound No. 5 of formula:

O O

He Ph I '' '' 'H25iC 12H25 C12HuS

C48H7604P2; M = 779.086

  a) Preparation of the dibromide of 1,4-bis (3-

  dodecyldiphenylphosphoniopropoxy) benzene (compound No. 6) of formula: ## STR2 ## C12H25C12Hu

C60H86Br202P2; M = 1155.109.

  This preparation corresponds to the following scheme C 12 H 25 Br -1 DMF / No R 1: 2 2 Br '48 h to 1400 CCi 2 H 2 Cl 2 (compound 6) This is carried out under a pure and dry nitrogen atmosphere. 0.47 ml of 1-bromododecane (1.96 mmol) and 0.4 g of 1,4-bis (3-diphenylphosphinopropoxy) benzene (0.69 mmol) in 50 ml of dimethylformamide are introduced into a 100 ml bicol with a condenser. anhydrous. The mixture is heated at 140 ° C. for 48 hours and then precipitated in hexane to give (after drying under p = 1 mm)

  Hg / P 2 O 5 / 2h) 0.60 g of pale yellow solid.

  The yield is 82%. Identification

Mp: 56-57 ° C

  pale yellow solid 1 H NMR (250 MHz, CDCl 3, C = 0.05 M) δ 0.82 (t, 6 H, 2 CH 3, J = 6 Hz); 1.15 (s wide, 32 H, 16 internal CH2); 1.47 (s, 8H, 4 internal CH2); 3.16 (s; 4H; 2 CH 2 -P +); 3.41 (s, 4H, 2 CH 2 -P +); 4.02 (brs; 4H; 2 CH2O); 6.66 (s; 4H; H hydroquinoneic); 7.6-7.9 (m; 20H;

aromatics).

  31 P NMR (81 MHz, CDCl 3, C = 0.05M) 628.6 (s). IR (KBr) 455 m - 600 m - 690 F - 710 m - 735 F - 765 F - 805 f_

  845 ff - 860 ff - 890 ff - 930 ff - 1000 m - 1030 ff -

  1070 ff - 1090 f - 1120 F - 1160 m - 1180 ff - 1225 ff - 1240 ff - 1320 ff - 1340 ff - 1380 ff - 1400 m - 1435 F - 1460 m - 1485 m - 1590 m - 1820 ff - 1905 ff - 2800

  f - 2860 GB - 2930 GB - 3010 e - 3060 e.

  b) Preparation of 1,4-bis (3-dodecylphenylphosphinopropoxy) benzene dioxide. This preparation corresponds to the following reaction scheme: 3 (31 NaOH [B = zen-H 2 O

21 (': 21'

  (Compound No. 6) (Compound No. 5) 0.1 ml of NaOH (4.68 mmol) in 1 ml of water and 0.54 g of the 1,4 bis dibromide are introduced into a 100 ml bicol with a condenser ( 3-dodecylbiphenyl phosphoniopropoxy) benzene (0.468 mmol) (compound No. 6) obtained above and 40 ml of benzene. The mixture is refluxed (75 ° C.) for 86 h and then it is diluted with water, decanted and extracted with chloroform; the organic phases are combined, washed with water, dried over Na 2 SO 4 and the solvent is then removed on a rotary evaporator. 0.29 g of white solid is obtained which after recrystallization (benzene / hexane) gives 0.17 g of white compound (dried under p = 0.1 mm Hg / P 2 O 5/6 h). The

yield is 47%.

  Identification White solid F = 67-68 C (benzene / hexane) 1 H NMR (200 MHz, CDCl 3, C = 0.07 M) δ 0.87 (t, 6 H, 2 CH 3, H = 6 Hz); 1.1 - 2.25 (m, 52H, 26 CH 2); 3.89 (t, 4H, 2 CH 2 O, J = 4.6 Hz); 6.72 ppm (s; 4H; H hydroquinoniques); 7.26 - 7.5 (m

  6H; meta and para); 7.6 - 7.8 (m, 4H, ortho H).

31 P NMR (81 MHz, CDCl 3, C = 0.07 M)

6 41.0 (s).

13 C NMR (50.3 MHz, CDCl 3, C = 0.24 M)

  13.98 (s; CH3); 21.24 - 21.32 - 21.63 - 21.70 -

  22.53 - 25.65 - 27.02 - 28.91 - 29.17 - 29.39 - 29.44 -

  66 - 30.77 - 30.94 - 31.74 (m; CH 2); 68.13 (d: CH 2 O, J = 13.9 Hz); 115.21 (s; hydroquinonic ortho); 128.51 (d = meta; J = 11.1 Hz); 130.27 (d = ortho; J = 8.8 Hz); 131.41 (d = J = 2.7 Hz); 132.19 (d = ipso; J = 92.2 Hz); 152.76 (s; C

hydroquinone ipso).

  Centesimal analysis (dried h / P 2 O 5 / mm Hg) C H o Calculated 74.00 9.83 8.21 Found 72.84 10.17 8.28 Mass: IE M = 778; m / z = 336 IR (KBr) 460 ff - 520 ff - 550f - 695 f - 720 f - 743 f - 795 ff

  - 823 f - 847 ff - 910 ff - 1020 f - 1070 f - 1114 m -

  1161 F - 1169 F - 1241 F - 1260 ff - 1305 ff - 1382 ff - 1407 ff - 1437 f - 1470 m - 1472 m - 1512 F - 1590'ff

  - 2335 ff - 2360 ff - 2851 GB - 2921 GB - 2954 GB.

  Example 4: Preparation of 5,13-dioxide of 5,13-

  didodecyl-1,9-dioxa-5,13-diphosphacyclohexadecane (Compounds Nos. 7 and 8) of Formula: C2H25-P = OO = P-Cl2H25 O

C34H7404P2; M = 632.936

  a) Preparation of 5,13-didodecyl-5,13-diiodide

  diphenyl-1,9-dioxa-5,13-diphosphonia cyclohexadecane (Compound No. 9)

O 21

p 21 '

C 12H25 / 12H25

C48H841202P2; M = 1008.959

  This preparation corresponds to the following reaction scheme: (Compound No. 9) It is carried out under a pure and dry nitrogen atmosphere. 250 g of isobaric dropping funnel 0.95 g (3.65 mmol) of bis (3-bromopropyl) ether and 2.44 g (3.65 mmol) of 4-oxa-1,7-heptamethylene bis dodecylphenylphosphine are introduced into 200 ml of anhydrous chloroform. ; in a first tricolor of 11, 400 ml of anhydrous chloroform and 400 ml of dimethylformamide and 100 ml of anhydrous chloroform are introduced into a second batch of 11 ml. The second tricol is raised to 1350C. The chloroform flows from the first three-necked to the second three-necked with a peristaltic pump (200ml / h) and the second three-necked to the first three-necked distillation. When distillation is well established, the slow addition of reagents from the ampule into the first three-neck is started (3h) and the cycle is continued for 48h. The mixture

reaction becomes brown.

  The pump is stopped and the CHCl 3 is allowed to distil, then the second tricolor is cooled, the mixture is concentrated on a rotary evaporator, the brown paste obtained is taken up in 50 ml of CHCl 3 and washed with 3 times four equivalents of NaI. Precipitate in hexane and give 3.12 g of brown precipitate. The precipitate obtained is recrystallized from CHCl 3 / AcOEt then slow diffusion of hexane and provides (after drying under p = 1 mm Hg / P 2 O 5 / 4h) 2.10 g of beige powder. The yield is 57%. Identification F = 172-174 ° C (CHCl 3 / AcOEt / hexane-Leitz) 1 H NMR (250 MHz, CDCl 3, C = 0.8M)

  0.86 (t, 6H, 2 CH3, J = 6.5 Hz); 1.23 (s) and 1.4 -

  2.15 (m, 48 H, 24 internal CH2); 2.65 - 3.85 (m, 20H, 4 CH2O and 6 CH2P +); 7.65 - 7.75 (m; 6H, meta and

para); 7.9 - 8.05 (m, 4H, ortho).

  31 P NMR (81 MHz, CDCl 3, C = 0.06 M) 6 32.32 (s) and 32.46 (s) (same integration - present)

both cis and trans isomers).

  13 C NMR (50.3 MHz, J mod, CDCl 3, C = 0.09M)

  13.90 (s, CH 3); 69.15 (d, J = 10 Hz, CH 2 -O); 16.81 -

  17.06 - 17.78 - 18.06 - 21.15 - 21.71 - 21.79 - 21.91 -

  22.41 - 22.53 - 28.75 - 28.78 - 29.05 - 29.93 - 29.32 -

  , 15 - 30,22 - 30,45 - 30,53 (m; CH2 internal and CH2-

  P + of each cis and trans isomer); 117.33 (d, J = 79.1 Hz, 1 ipso); 117, 40 (d, J = 80 Hz, 1 C ipso); 130.09 (d, J = 11.8 Hz, meta); 132.26 (d, J = 9.3 Hz, ortho); 132.35 (d, J = 8.9 Hz, ortho); 134.11 (s, para). Mass: FAB (Noba): [M- (I -)] + = 881; m / z = 138 IR (KBr) 430 ff - 495 ff - 690 f - 745 m - 835 ff - 930 ff - 975 ff - 1000 ff - 1030 f - 1050 f - 1100 F - 1117 F - 1160 f - 1185 ff - 1220 f- 1280 ff- 1345 ff - 1360 ff - 1375

  ff - 1400 f - 1435 m - 1460 f - 1590 ff - 2855 FF -

2920 FF - 3010 ff.

  Centesimal analysis (after drying under p = 0.11 mm Hg / t = 80 C / P 2 O 5 / 24h) C H 0 Calculated 57.13 8.39 3.17 Found 57.43 8.19 3.90

  (b) Preparation of 5,13-didodecyl 5,13-dioxide

  1,9-dioxa-5,13-diphosphacyclohexadécane. This preparation corresponds to the following reaction scheme: ## STR1 ## In a 25 ml bicol with a condenser, 0.59 g (14.7 mmol) of NaOH are introduced into 2.9 ml of water,

* 1.48 g (1.47 mmol) of 5,13-didodecyl-5,13-diiodide

  diphenyl-1,9-dioxa-5,13-diphosphoniacyclohexadécane

  (Compound No. 9) obtained previously and 15 ml of ethanol.

  Refluxed (80 C) for 72h. It is spread with water and the ethanol / water azeotrope is removed on a rotary evaporator. It is diluted with water and chloroform, decanted and extracted with chloroform; the organic phases are combined, washed with water until neutral, dried over Na 2 SO 4 and the solvent is then removed on a rotary evaporator. After drying under p = 1 mmHg / P 2 O 5 / 4h, 92 g of beige brown solid are obtained. An analysis in 31p NMR shows the unique presence

  of both cis and trans stereoisomers.

The yield is 92%.

  Chromatography on Lobar (eluent AcCEt / MeOH / 15) to separate the two isomers and then

  recrystallized from benzene / hexane.

  Both isomers have the following characteristics: A. Alpha isomer of formula: C_9o

C12HU "-P = O = P C12H2

O

(compound 7)

C34H7404P2; M = 632.936

  Identification of the alpha isomer White solid

  M.p. 115-116 ° C (Leitz - benzene / hexane).

  Rf = 0.1 (SiO2 - AcOEt / MeOH 80/20-I2) -

  1H NMR (250 MHz, CDCl 3, C = 0.06M) δ 0.87 (t, 6H, 2 CH 3, J = 6.5 Hz); 1.24 (bs) and 1.5-1.7 (m) and 1.75-1.9 (m) (60H, CH 2 CH 2, CH 2 CH 2 and CH 2 -P = O); 3.4 - 3.5 (m;

8H; 4 CH2-O).

  31 P NMR (81 MHz, CDCl 3, C = 0.13 M) δ 50.02 (s) 13 C NMR (50.3 MHz, CDCl 3, C = 0.09 M)

  6 14.00 (s; CH 3); 21.23 - 21.31 - 22.42 - 22.49 -

  22.56 - 23.60 - 24.91 - 29.04 - 29.21 - 29.28 - 29.46 -

  29.49 - 30.92 - 31.19 - 31.78 (m; CH2 internal and CH2-

P = O); 70.29 (d, J = 12.6 Hz, CH 2 O).

  IR (KBr) 738 f - 755 f - 772 f - 815 f - 832 f - 850 ff - 870 ff

  - 918 ff - 930 ff - 977 f - 1017 f - 1032 f - 1060 f -

  1095 F - 1117 F - 1150 FF - 1182 m - 1210 m - 1220 m -

  1260 f - 1290 ff - 1320 ff - 1345 f - 1365 f - 1408 f -

  1435 f - 1462 m - 2775 f - 2855 FF - 2915 FF.

  Centesimal analysis (dried under p = 0.02 m Hg / t = 60 C / 48h / P205)

C H O

  Calculated 68.32 11.78 10.11 Found 68.68 11.51 10.03 Mass: EI M = 632 - m / z = 317 B. Beta isomer of formula:

C 12HU _'P = O O = P- C12H

C '.z $ 0 \ O --P I _T (compound no. 8)

C34H7404P2; M = 632.936

  Identification of the beta isomer White solid F = 128.5-129 ° C (Leitz benzene / hexane) Rf = 0.36 (SiO 2 -AcOEt / MeOH 80/20-I 2) 1H NMR (250 MHz; CDCl 3; C = 0.06 M) 6 0.87 (t, 6H, 2 CH 3, J = 6.5 Hz); 1.24 (bs) and 1.5-1.7 (m) and 1.75-1.9 (m) (60H, CH 2 CH 2, CH 2 CH 2 and CH 2 -P = O); 3.4 - 3.5 (m;

8H; 4 CH2-O).

  31 P NMR (80 MHz, CDCl 3, C = 0.13 M) 6 49.61 (s) 13 C NMR (50.3 MHz, CDCl 3, C = 0.09 M)

  13.88 (s; CH3); 21.28 - 21.36 - 22.42 - 22.54 -

  23.71 - 25.02 - 27.88 - 29.04 - 29.19 - 29.26 - 29.44 -

  29.48 - 30.79 - 30.92 - 31.19 - 31.76 (m; CH2 internal

  and CH2-P = O); 70.29 (d, J = 12.2 Hz, CH 2 -O).

  IR (KEr) 715 m - 755 ff - 770 m - 805 m - 835 f - 870 f - 880 f

  - 890 ff - 900 ff - 927 ff - 960 f - 972 f - 982 f -

  1010 f - 1030 f - 1055 ff - 1080 f - 1105 FF - 1145 GB -

  1170 F - 1198 f - 1210 m - 1225 m - 1235 m - 1260 ff - 1285 ff - 1325 ff 1355 ff - 1375 ff - 1410 f - 1435 f

  - 1450 f - 1470 m - 1482 f - 2860 FF - 2915 FF -

2960 F.

  Centesimal analysis (dried under p = 0.02 mmHg / t = 60 C / 48h / P205)

C H O

  Calculated 68.32 11.78 10.11 Found 68.68 11.71 10.41 Mass: EI

M = 632 - m / z = 317.

  Example 5 Preparation of 4-oxa-1,7-dioxide

  heptamethylene bis (2'-ethoxyethyl) phenylphosphine (compound No. 10) of formula: ## STR1 ##

C26H4005P2; M = 494.553

  a) Preparation of the diiodide of 4-oxa-1,7-

  heptamethylene bis (2'-methoxyethyl) diphenylphosphonium (compound n 11) of formula: Pp 0 / Pph, 2 1 / O

C38H461203P2; M = 842.520

  This preparation corresponds to the following reaction scheme:

DMF / NZ

  P10 hP ^ \ / xPO ^ \ 'Pphl 70b at 100oC b- Ph p Ph-21 b. Nal (compound 11) It is carried out under a pure nitrogen and dry atmosphere. In a 100ml bicol with a condenser, 0.74ml (7.66mmol) of 2-bromoethyl methyl ether and 1.20g (2.56mmol) of 4-oxa-1,7-heptamethylene bis diphenylphosphine are introduced into 50ml. anhydrous dimethylformamide. It is heated at 100 ° C. for 70 hours and then an ion exchange is carried out by successive washing with an aqueous solution of 25.5 mmol of NaI. It is precipitated in ether and a very hygroscopic white powder is obtained which quickly takes on the appearance of a brown paste. After drying under p = 1 mmHg / P205 / 24h, we have 2.3 g

paste.

The reaction is quantitative.

  Identification brown paste NMR31p (81 MHz, CDCl3, C = 0.07) 8 30.07 (s) 1 H NMR (200 MHz, CDCl3, C = 0.07) 6 1.14 ppm (t, 4H, 2 internal CH2) J = 7 Hz);

  1.65-1.85 (m; 4H; 2H 2 O); 3.01 (s; 6H; 2 CH3-

  O); 3.3-3.65 (m; 16H; 4 CH 2 -O and 4 CH 2 -P +); 7,55-

  7.75 (m, 12H, meta and para); 7.85-8.0 (m; 8H; ortho).

  (b) Preparation of 4-oxa-1,7-dioxide

  heptamethylene bis (2'-ethoxyethyl) phenylphosphine.

  This preparation corresponds to the following reaction scheme: ## STR2 ## ## STR2 ##

<>

  (Compound No. 11) (Compound No. 10) In a 50ml bicol equipped with a condenser, 0.89 g (22.3 mmol) of NaOH are introduced into 4.5 ml of water,

  1.88g (2.23mmol) of 4-oxa-1,7-diiodide

  heptamethylene bis (2'-methoxyethyl) diphenylphosphonium

  (compound No. 11) obtained above and 30 ml of ethanol.

  The mixture is refluxed (79 ° C.) for 4 days and then it is diluted with water, the azeotrope is removed on a rotary evaporator and then the mixture is extracted with chloroform; the organic phases are combined, washed with water, dried over Na 2 SO 4 and the solvent is then removed on a rotary evaporator. We

gets 1.08g of yellow oil.

  A 31 P NMR study shows the presence of the product at about 58% as well as that of another phosphine oxide.

The yield is 58%.

  It is chromatographed on lobar (eluent AcOEt / MeOH / 20) and a white solid is obtained, inter alia.

  (After drying under p = 1 mmHg / P205 / t = 40 C / 24h).

  Identification White solid F = 73-740 C (Leitz) 1 H NMR (200 MHz, CDCl 3, C = 0.12 M) δ 1.11 (t, 3H, CH 3, J = 7 Hz); 1.12 (t, 3H, CH 3, J = 7 Hz); 1,6 - 2,4 (m; 12 H; 4 CH2-P = 0 and 2 internal CH2); 3.25 - 3.80 (m; 12H; 6 CH 2 -O); 7.4 - 7.55 (m, 6H, meta and para); 7.6 - 7.75 (m, 4H ortho). 31 P NMR (81 MHz, CDCl 3, C = 0.08 M)

6 41.15 (s).

  13 C NMR (50.3 MHz, CDCl 3, C = 0.25 M) δ 14.85 (s, 2 CH 3); 21.62 (d, internal CH2, J = 3.9 Hz); 27.04 (d, CH 2 -P = 0, J = 69.8 Hz); 31.06 (d, CH 2 P = 0, J = 67.4 Hz); 63.52 (d, CH 2 O, J = 1.9 Hz); 66.05 (s, Me-CH 2 -O); 70.29 (d, CH 2 O, J = 14.8 Hz); 128.42 (d = meta; J = 11.3 Hz); 130.12 (d ortho, J = 9.0 Hz); 131.44 (d: J = 2.7 Hz)

132.15 (d = ipso; J = 83.8 Hz).

  IR (KBr) 427 ff - 455 ff - 475 ff - 515 ff - 547 F - 697 F - 720

  m - 744 F - 780 m - 830 ff - 842 ff - 888 ff - 925 ff -

  975 ff - 1000 ff - 1012 m - 1035 f - 1050 f - 1070 m -

  1113 FF - 1127 F - 1168 FF - 1220 m - 1260 ff - 1280 ff - 1315 ff - 1350 f 1370 m - 1410 f - 1432 m - 1450 f - 1470 ff - 1482 ff - 1590 ff - 2800 m 2868 GB - 2928

  m - 2946 m - 2976 m - 3060 ff - 3080 ff.

Centesimal analysis

C H O

  Calculated 63.15 8.15 16.18 Found 63.22 8.29 16.06 Mass: FAB (matrix used: NOBA)

(M + H) + = 495.

IE

M + = 494 - m / z = 255.

  Example 6 Preparation of 4-oxa-1,7-dioxide

  heptamethylene (2-ethoxyethyl) phenylphosphine diphenylphosphine (compound No. 12) of formula:

O O

  / C28H3604P2; M = 498r544 This preparation corresponds to the following reaction scheme:

O O

? ' o'N '21-NaOH

H2 0-EOH

o o / 4d to 790c

>

  (Compound No. 11) (Compound No. 12) In a 50ml bicol equipped with a condenser, 0.89 g (22.3 mmol) of NaOH is introduced into 4.5 ml of water,

  1.88 g (2.23 mmol) of the 4-oxa-1,7-diiodide

  heptamethylene bis (2-methoxyethyl) diphenylphosphonium (compound No. 11) obtained in Example 5a) and 30 ml of ethanol. The mixture is refluxed (79 ° C.) for 4 days and then it is diluted with water, the azeotrope is removed on a rotary evaporator and the mixture is extracted with chloroform; the organic phases are combined, washed with water, dried over Na 2 SO 4 and the solvent is removed on

  Rotary evaporator. 1.08 g of yellow oil is obtained.

  A 31 P NMR study shows the presence of the product at about 38% as well as that of another phosphine oxide.

The yield is 38%.

  It is chromatographed on lobar (eluent AcOEt / MeOH 80/20) and a yellowish paste is obtained, which tends to crystallize (after drying under p = 1 mm Hg / P 2 O 5 / t = 40 C / 24h). Identification Yellowish paste 1 H NMR (200 MHz, CDCl 3, C = 0.12 M) δ 1.07 (t, 3H, CH 3, J = 7 Hz); 1, 55 - 2.4 (m; H; 3 CH2-P = 0 and 2 internal CH2); 2.51 (s; 1H;

  0.5 H2O); 3.25 - 3.80 (m; 8H; 4 CH 2 -O); 7.35 -

  7.55 (m, 9H, meta and para); 7.6 - 7.75 (m, 6H;

ortho).

31 P NMR (81 MHz, CDCl 3, C = 0.08 M)

  - 33.31 (s); 39,45 (s) about the same integration.

  13 C NMR (50.3 MHz, CDCl 3, C = 0.29 M) δ 14.86 (s, CH 3); 21.65 (d; internal CH2; J = 3.9 Hz); 21.77 (d; internal CH2; J = 3.6 Hz); 26.20 (d, CH 2 P = 0, J = 73.0 Hz); 27.02 (d, CH 2 -P = 0, J = 69.7 Hz); 31.06 (d, CH 2 -P = 0, J = 67.4 Hz); 63.51 (d, CH 2 O, J = 2.1 Hz); 66.08 (s; Me-CH 2 -O); 70.20 (d, CH 2 O, J = 14.6 Hz); 70.29 (d, CH 2 O, J = 14.8 Hz); 128.47 (d = meta; J = 10.6 Hz); 128.48 (d, 2 meta, J = 11.6 Hz); 130.13 (d, ortho; J = 9.1 Hz); 130.56 (d, 2 ortho; J = 9.3 Hz); 131.49 (d, J = 3.0 Hz); 131.55 (d, 2 para, J = 2.9 Hz); 132.08 (d = ipso; J = 93.7 Hz); 132.74 (d;

2 ipso; J = 98.5 Hz).

  On another spectrum, the 2 C ipso were differentiated: 132.73 (d, ipso, J = 98.4 Hz); 132.74 (d, ipso, J = 98.5 Hz) IR (KBr) 696 F - 720 m - 775 m 800 m - 995 f - 1025 f - 1075 m - 1106 FF - 1112 FF - 1183 F - 1260 f 1312 ff - 1355 f - 1405 f - 1438 m - 1490 f - 1595 ff - 1665 f - 2335 f 2360 f - 2800 f - 2867 f - 2930 f - 2975 f - 3060 f

- 3390 m.

Mass: EI

M = 498 - m / z = 258.

Centesimal analysis: M + 1,3H20

C H

  calculated 64.43 7.45 found 64.36 7.43

  Example 7 Preparation of 1,4-bis (3- (3'-dioxide)

  methoxypropyl) phenylphosphinopropoxy)] benzene (compound 13) of the formula: o0 0 o0

C32H4406P2; M = 586.644

  a) Preparation of the diiodide of 1,4-bis [3- (3'-

  methoxypropyl) diphenylphosphoniopropoxy] benzene (compound No. 14) of formula:

/ h 0> 21-

/ O \

C44H541204P2; M = 962.669

  This preparation corresponds to the following reaction scheme: a / o / a. B / I DMF / 2 Pph 2ozzOv z3 j at 700Cr PPh * 2 1

/%% /. 2

b. Nai

O O

  (Compound No. 14) It is carried out under a pure nitrogen and dry atmosphere. In a bicol of 100 ml equipped with a condenser, 0.24 g of 1-bromo-3-methoxypropane (1.56 mmol) and 0.29 g of 1,4-bis (3-diphenylphosphinopropoxy) benzene are introduced.

  (5.15 x 10 -4 mol) in 70 ml of anhydrous dimethylformamide.

  It is heated at 70 ° C. for 3 days and then an ion exchange is carried out by successive washings with an aqueous solution of 3.6 mmol of NaI. The mixture is precipitated in ether and (after drying under p = 1 mm Hg / P 2 O 5 / 4h), 0.51 g of

  Hygroscopic crude containing 5% ether.

The gross yield is 98%.

  The phosphonium salt will be used as is for

the following.

  Hygroscopic solid identification 1 H NMR (200 MHz, CDCl 3, C = 0.7 M)

  1.18 (t, 4H, CH 3 ether, J = 7 Hz); 1.75 -

  2.10 (m; 8H; 4 internal CH2); 3.10 - 3.80 (m, 20.6 H, 2 O-CH 3, 2 CH 2 -O, 4 CH 2 -P + and CH 2 ether); 4.0 - 4.20 (m; 4H; 2 CH 2 -OPh); 6.60 - 6.80 (m; 4 H; hydroquinone); 7.50 - 8.0 (m, 20H, aromatics). 31 P NMR (81 MHz, CDCl 3, C = 0.7 M) 6 29.05 (s; 29.06 (s) 13 C NMR (50.3 MHz, CDCl 3, C = 0.7 M, J modulated) 18.30 (internal CH 2, J = 2.7 Hz); 19.35 (s; internal CH2); 22.47 (d, CH 2 -P +, J = 20.5 Hz); 22.16 (d, CH 2 -P +, J = 21.1 Hz); 58.60 (s; O-CH 3); 66.76 (d, CH 2 O, J = 16.3 Hz); 70.66 (d, CH 2 O, J = 15.1 Hz); 115.46 (s; hydroquinone hydrochloric acid); 117.61 (d = ipso; J = 83.3 Hz); 130.34 (d = meta; J = 10.2 Hz); 132.88 (d, ortho; J = 9.6 Hz); 134.82 (d;

  para; J = 2.9 Hz); 152.33 (s, hydroquinone).

  The Cs of ethyl ether are observed as well as

  some secondary peaks at the aromatic C level.

- Mass: FAB (NBA [M- (I -)] + = 835

  b) Preparation of 1,4-bis (3- (3'-dioxide)

  methoxy-propyl) phénylphosphinopropoxy) benzene. This preparation corresponds to the following reaction scheme: NaOH / Benzine-H.O.

/ \ / 0O

  (Compound No. 14) (Compound No. 13) It is carried out under a pure and dry nitrogen atmosphere. In a bicol of 100 ml provided with a condenser, 0.20 g of NaOH (4.7 mmol) is introduced into 2 ml of water and

0.45 g of 1,4-bis (3- (3'-diiodide)

  methoxypropyl) diphenylphosphoniopropoxy) benzene (4.44 × 10 -4 mol-Pm = 95%) (compound No. 14) previously obtained in 25 ml of benzene. Refluxed (70 ° C.) for 24 hours, decanted, the organic phase washed with water until neutral, dried over Na 2 SO 4 and obtained (after drying under p = 1 mm).

  Hg / P 2 O 5 / 4h) 0.27 g of oil which tends to crystallize.

The reaction is quantitative.

  1 H NMR (200 MHz, CDCl 3, C = 0.1 M) identification

  8 1.60 - 2.30 (m; 16 H; 4 internal CH2 and 4 CH2-

  P = O); 3.00 - 3.50 (m; 10 H; 2 O-CH 3 and 2 CH 2 -O); 3.70 - 4.00 (m; 4H; 2 CH 2 -O); 6.60 - 6.80 (m; 4 H; hydroquinone); 7.40 - 7.60 (m, 6H, para);

7.60 - 8.0 (m, 4H, ortho).

31 P NMR (81 MHz, CDCl 3, C = 0.1 M) =

41.18 (s).

  13 C NMR (50.3 MHz, J modulated, CDCl 3, C = 0.7 M) 6 21.68 (d, internal CH 2, J = 3.8 Hz); 26.58 (d, CH 2 -P = 0, J = 69.3 Hz); 26.64 (d, CH 2 -P = 0, J = 69.8 Hz); 58.35 (s; O-CH 3); 68.14 (d, CH 2 O, J = 13.9 Hz); 72.30 (d, CH 2 O, J = 14.2 Hz); 115.26 (s; hydroquinone hydrochloric acid); 128.60 (d, meta; J = 11, 2); 130.35 (d = ortho; J = 8.9 Hz); 131.55 (d, para; J = 2.8 Hz); 131, 93 (d, ipso; J = 93.0 Hz); 152.80

(s, C-O hydroquinones).

IR (KBr)

  460 f - 487 m - 500 F - 515 F - 545 F - 690 F - 710 m -

  720 F - 738 GB - 752 GB - 765 GB - 798 e - 875 m - 905 f -

  930 ff - 995 m - 1002 m - 1030 ff - 1052 f - 1065 f -

  1110 FF - 1160 f - 1190 ff - 1215 m - 1270 ff - 1295 ff

  - 1320 f - 1340 f - 1350 f - 1382 f - 1410 e - 1435 GB -

  1482 m - 1588 m - 1610 ff - 1680 ff - 1780 ff - 1830 ff - 1920 ff - 1985 ff - 2020 ff - 2800 m - 2830 m - 2865 F - 2890 F - 2920 m - 2980 m - 3000 f - 3040 ff - 3050

ff - 3080 ff.

  Example 8 Preparation of 1,4-bis (3-dioxide

  diphenylphosphinopropoxy) benzene (compound No. 15) of formula: ## STR2 ##

C36H3604P2; M = 594.63

  a) Preparation of the dibromide of 1,4-bis (3-

  triphenylphosphoniopropoxy) benzene (compound No. 16) of formula: ## STR1 ## This preparation corresponds to the following reaction scheme: DMF / N 2 Br 2 pp3. Br 3 O 3 / B 16h at 140 ° C. (Compound No. 16) It is carried out under a pure nitrogen atmosphere and dry. In a 250 ml bicol with a condenser, 3.87 g of 1,4-bis (3-bromopropoxy) benzene (10.99 mmol), 7.87 g of triphenylphosphine (30 mmol) and ml of anhydrous dimethylformamide are introduced. It is heated at 140 ° C for 16 hours. It is concentrated on a rotary evaporator, taken up in a few ml of MeOH and precipitated in ether. A white solid is obtained which is recrystallized in CHCl 3 (and a few drops of MeOH) / AcOEt. We obtain (after drying under 0.1 mm Hg / P 2 O 5 / 4h)

  8.03g of white crystals (9.96mmol).

  The yield is 90% Identification F = 268 C (CHCl3 (and a few drops of MeOH) / AcOEt) NMRH (250 MHz, CD3OD, C = 0.07M) 6 2 - 2.2 (m; 4H; 2 CH2) internal); 3.45 - 3.65 (m; 4H; 2 CH 2 -P +); 4.05 - 4.15 (m; 4H; 2 CH 2 O); 6.8 (s; 4H; O-Ph-O); 7.65-7.90 ppm (m; 30 H; aromatics). 31 P NMR (81 MHz, CD 3 OD, C = 0.07M) 6 24.36 (s) IR (KBr) (after drying under p = 0.1 mm Hg / t = 80 C / P 2 O 5 / 24h 435 f - 465 f - 500 F - 510 GB - 538 GB - 612 ff - 690 GB

  - 720 FF - 745 FF - 822 m - 840 f - 915 ff - 940 ff -

  995 m - 1040 F (shouldered) - 1070 f - 1110 FF - 1160 f -

  1182 m - 1230 FF - 1280 f - 1308 ff - 1345 ff - 1370 ff - 1410 m - 1430 FF - 1475 F - 1508 FF - 1585 m - 1620

  ff - 1830 ff - 1910 ff - 2790 f - 2860 m - 2880 m -

2960 f - 2980 ff - 3000 f - 3050 f.

  b) Preparation of 1,4-bis (3-dioxide)

  diphénylphosphinopropoxy) benzene. This preparation corresponds to the following reaction scheme: ## STR2 ## 3.5 g of NaOH (87.6 mmol) are introduced into 17.5 ml of water,

7.38g of dibromide of 1,4-bis (3-

  triphenylphosphoniopropoxy) benzene (9,15mmol) (compound No. 16) obtained above and 80 ml of ethanol. Refluxed (78 C) for 48h. It is spread with water, the azeotrope is removed on a rotary evaporator, decanted, extracted with CHCl 3; the organic phases are combined, washed with water, dried over Na 2 SO 4 and the solvent is then removed on a rotary evaporator. A solid is obtained which is recrystallized from benzene (and

a few drops of CHCl3) / hexane.

  We obtain (after drying under p = 0.5mm

  Hg / P205 / 24h) 4.48 g of white powder.

- The yield is 82%.

Identification

White solid.

  Mp = 183 ° C (benzene / hexane) 1H NMR (200 MHz, CDCl 3, C = 0.11 M), 1.9 - 2.2 (m, 4H, 2 internal CH 2); 2,3 - 2,6 (m; 4H; 2 CH 2 -P = O); 3.94 (t; 4H; 2 CH 2 -O; J = 5.8 Hz); 6.74 (s; 4H; O-Ph-O); 7.2 - 7.6 (m, 12H;

  meta and para); 7.6 - 7.8 (m, 8H, ortho H).

31 P NMR (81 MHz, CDCl 3, C = 0.11M)

6 33.2 (s).

  IR (KBr) 410 f - 468 ff - 510 F - 550 FF - 690 F - 720 F - 730 m - 745 F 760 m - 780 ff - 790 ff - 820 m - 835 m - 910 f - 915 ff - 940 ff - 1000 m - 1015 m - 1025 F - 1065 m - 1110 m - 1118 F - 1185 FF - 1220 FF - 1240 FF - 1285 m - 1300 ff - 1330 f - 1390 m - 1405 ff - 1435 GB - 1470

  m - 1505 FF - 1590 ff - 1625 ff - 1890 ff - 1960 ff -

  2870 m - 2910 m - 2930 m - 2950 m - 3000 ff - 3050 f -

3070 f.

  Centesimal analysis (dried 24 h / p = 0.5 mm Hg / 20 C) ______________________________________ Calculated 72.72 f6.10 f10.76 Found 72.49 6.30 10.92 Mass: FAB (matrix used: NOBA)

(M + H) + = 595.

Examples 9 to 17.

  In these examples, the effectiveness of the diphosphine dioxides of Examples 1 to 8 for the extraction of plutonium, neptunium and americium is evaluated.

  an aqueous solution containing one of these elements.

  The composition of the aqueous solution is as follows: HNO 3: 1 mol / l NaNO 3: 4 mol / l pH: 0 Pu: 0.6 mg / l Am: 0.02 mg / l Np: 200 mg / l In these examples, 3ml of the aqueous solution is brought into contact with 3ml of an organic solution consisting of nitrophenyloctyl ether containing 0.01mol / l of the diphosphine dioxide used. The contacting is carried out in a tube in

  polypropylene of 20ml which is subjected to agitation.

  After lh of contacting, the two phases are allowed to settle and the activity of each phase is counted by

liquid scintillation.

  The distribution coefficient D, which corresponds to the ratio of the activity of the actinide in the organic phase to the activity of the actinide in the aqueous phase, is then determined. The percentage of actinide extracted in the organic phase is also determined by the relation:% of actinide extract - = 1 + D The extractants used as well as the results obtained for the extraction are given in Table 1

following.

  The actinides extracted in the organic phase are then re-extracted by bringing this phase into contact with 3 ml of an aqueous reextraction solution consisting of a solution of oxalic acid at 0.5 mol / l or an aqueous solution of trisodium citrate at 0.25 mol. / 1. The results obtained for the reextraction as well as the reextraction solution used are also

given in Table 1.

  In this table, the results obtained were also given for comparison when the CMPO is used for the extraction at a concentration of 0.

in nitrophenyl hexyl ether.

  In view of these results, we note that all the oxides tested extract more than 90% of the plutonium and also the neptunium with good yields. In contrast, trivalent actinides such as americium are less extracted, which is not the case with the CMPO. Thus, the diphosphine dioxides of the invention have an efficiency comparable to that of the CMPO and they are more selective than the CMPO with respect to the actinides

trivalent.

Examples 18 to 24.

  In these examples, the second embodiment of the process of the invention is used for extracting neptunium and plutonium from aqueous solutions having the same compositions as those used in Examples 9 to 17. the device shown in the attached figure. This device comprises an enclosure 1 separated into two compartments 3 and 5 by a supported liquid membrane 7, constituted by a microporous polypropylene membrane marketed under the name CELGARD 2500 which has the following characteristics: Porosity factor: 0.45 Pore diameter: 0.04 pm

Thickness of the membrane: 0.025 mm.

  The pores of this membrane are filled with an organic phase consisting of nitrophenylhexyl ether

  comprising 0.01 mol / l of diphosphine dioxide.

  Both compartments 3 and 5 are equipped

magnetic stirrers 9.

  Compartment 3 contains 50 ml of the aqueous solution (NaNO 3: 4 mol / l, HNO 3: 1 mol / l with Pu or Np) and the compartment 5 contains 50 ml of an aqueous reextraction solution consisting of an aqueous solution of

0.25 mol / l of trisodium citrate.

  The two solutions are stirred, and the initial activity of the compartment 3 solution is determined, followed by the activity of the aqueous compartment 5 reextraction solution by liquid spectrometry, and the operation is continued for several days. The percentage of neptunium and plutonium recovered in the aqueous stripping solution after 24 h is deduced as well as the maximum

backwashed.

  The phosphine oxides used, the permeability of the membrane to Np and Pu, as well as the% after 24 hours and the maximum% of Np and Pu recovered are

given in Table 2.

  In view of this table, it can be seen that the supported liquid membrane is very effective in separating Np and

  Pu in the aqueous stripping solution.

Table 1

  Prepared in Extraction Re-extraction Prepared in Ex. Compound Example DPu% Pu DAm DNp% Np solution Dpu DNp extract extract 9 N 1 1 20 95.2 0.05 0.9 47.4 Ac.oxali 0.03 0.05 0.01 M as 0.5 N 3 2 12 92, 3 0.04 0.5 33.3 Ac.oxali 0.01 0.03 0.01 M as 0.5 11 N 5 3 35 97.2 0.004 1.2 54.5 citrate 0.01 0.03

0.01 M 0.25M

  12 N 7 4 28 96.6 0.006 1.1 52.4 citrate 0.01 0.03 0.01 M 0.25 M r 13 N 8 4 41 97.6 0.01 1.8 64.3 citrate 0 , 01 0, 03

0.01 M 0.25M

  14 N 10 5 35 97.2 0.02 1.2 54.5 citrate 0.01 0.05

0.01 M 0.25M

  N 12 6 14.2 93.3 0.01 1 50 citrate 0.01 0.04

0.01 M 0.25M

  16 N 13 7 30 96.8 0.004 4.1 80.4 citrate 0.01 0.01

0.01 M 0.25M

  17 N 15 8 17 94.4 0.006 1 50 ac.oxali 0.005 0.05 0.01 M as 0.5 Ex CMPO Ph iB 22 95.6 1.2 0.85 45.9 citrate 0.003 0.004

E 0.01 M P 0.25 M

* E CHU O Coi O 0 BL c)

Table 2

  Permeability% reciRarA% maximum rAci] -

  Prepared in _.cm/h) in 24 hours Ex. Compound example Np Pu Np Pu Np Pu

18 N 1 1 0.62 2.47 35 95 41 98

19 N 3 2 0.231 2.37 23 80 38 85

N 5 3 1.43 1.95 51 72 60 87

21 N 7 4 0.837 2.17 55 83 73 90

22 N 8 4 0.84 3 40 84 47 86

23 N 10 5 0.1 0.37 21 66 45 80

24 N 12 6 0.1 0.94 20 72 60 90

  Ph iBu P compa- XB ratif 1 CMPO C8H7 0 BU 0.74 3.44 50 99 68 100 Ph Ce8 il 1 iB? 2 "octyl P C 1 p 7 0, 38 2.52 30 95 48 95 P110 NB '

Claims (19)

  1. Diphosphine dioxide corresponding to one of the following formulas: R O cLR3 P-Q-P (R) R2 R4 Q R-P = O O = P-R '(II)   In which: R1, R2, R3 and R4, which may be the same or different, represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from alkoxy, carboxy, hydroxy and amino; and aryl groups unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; - R and R 'which may be the same or different represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from alkoxy, carboxy, hydroxy and amino groups; aryl groups which are unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; Q and Q ', which may be identical or different, represent a group of formula: - (CH2) 1-,   - (CH2) m -CH = CH- (CH2) n-, - (CH2) mC = C- (CH2) n-, - (CH2) p- [O- (CH2) q] r-, (CH2) p- [S- (CH2) q] r-, - (CH2) p- [O-R5-O- (CH2) q] r-, or - (CH2) p- [N (R6) - (CH2) q] r-   wherein R5 is phenylene or a divalent group derived from a heterocyclic ring, R6 is H or alkyl, and 1, m, n, p, q and r are integers such that 3 <1 <16 3 <q <16 1 <m <16 1 <r <16 1 <n <16 3 <p <16 provided that   1) in formula I, Q does not represent - (CH2) 3-   O- (CH2) 3- or (CH2) 3-O- <- O- (CH2) 3- when R1, R2, R3 and R4 are all phenyl, or (CH2) 1 when R1, R2, R3 and R4 are all phenyl or benzyl, 2) in formula II, Q and Q 'do not represent   both (CH2) 3-0- (CH2) 3- or (CH2) 3-O- .-- O- (CH2) 3-   when R and R 'are both phenyl, and 3) in formula II, Q and Q' do not represent - (CH2) 1- when R and R 'are both phenyl or benzyl groups.   2. Diphosphine dioxide according to claim 1, characterized in that it is chosen from - 4-oxa-1,7-heptamethylene bis dodecylphenyl phosphine dioxide, - 1,8-octamethylene bis dodecylphenyl phosphine dioxide, - 1,4-bis (3-dioxide   dodécylphénylphosphinopropoxy) benzene,   - 5,13 - 5,13 - didodecyl-1,9-dioxa-5,13-dioxide diphosphacyclohexadécane,   4-oxa-1,7-heptamethylene bis (2'-dioxide)   ethoxyethyl) phenylphosphine, 4-oxa-1,7-heptamethylene (2'ethoxyethyl) phenylphosphine diphenyl phosphine dioxide, and 1,4-bis [3- (3'-dioxide)   methoxypropyl) phénylphosphinopropoxy] benzene. 3. Process for the preparation of diphosphine dioxide of formula: R ', 1 R3 P-Q-P (I) RZ // \ R4   in which R1, R2, R3, R4 and Q have the meanings given in claim 1, characterized in that it consists in subjecting a phosphonium disalt of formula R3 R2-pEQpE-R4,2X (III) to basic hydrolysis. ) R? R8   wherein R 1, R 2, R 3, R 4 and Q have the meanings given above, R 7 and R 8 are benzyl or phenyl groups and X is a halogen atom, to convert it to diphosphine of formula (I).   4. Process for the preparation of diphosphine dioxide of formula: Q R-P = O O = P-R '(II   In which R, R ', Q and Q' have the meanings given in claim 1, characterized in that it consists in subjecting to a basic hydrolysis a phosphonium disalt of formula: R Q PG (IV) 2x- R7 QI R8 / \   in which R, R, Q and Q 'have the meanings given above, R7 and R8 are benzyl groups or   phenyl, and X is a halogen atom. 5. Phosphonium disel of formula: R1 R3 R2-P-Q_R4,2X (III) R7 / R8   wherein - R1, R2, R3, R4 and Q have the meanings given in claim 1, R7 and R8 which may be the same or different, are benzyl groups or   phenyl and X is a halogen atom. 6. Formula phosphonium disel Q / -R ' PG pe (IV) 2X- R7 Q 'R8   wherein R, R ', Q and Q' have the meanings given in claim 1, R7 and R8 are benzyl or phenyl, and X is a halogen atom.   7. Disel according to any one of the claims   and 6, characterized in that X represents Br or I. 8. Phosphonium disel according to claim 5, characterized in that it is chosen from: - 4-oxa-1,7-heptamethylene bis dodecyl diphenyl phosphonium dibromide, 1,8-octamethylene bis dodecyldiphenyl phosphonium diiodide, 1,4-bis (3-dodecyldiphenyl phosphoniopropoxy) benzene dibromide,   4-oxa-1,7-heptamethylene bis (2'-diiodide)   methoxyethyl) diphenyl phosphonium, and 1,4-bis [3- (3'-methoxypropyl) diphenyl diiodide phosphoniopropoxy] benzene.   Phosphonium disel according to claim 6,   characterized in that it is the diiodide of 5,13-   didodecyl-5,13-diphenyl-1,9-dioxa-5,13-diphosphonia cyclohexadecane. 10. A process for separating the actinides or present in an aqueous solution, characterized in that it consists in bringing the aqueous solution into contact with an immiscible phase comprising at least one diphosphine dioxide corresponding to one of the following formulas: R1 O O R3 I I) P-Q-P (I) R2 / R4 R-P = O O = P-R '(II)   In which: R1, R2, R3 and R4, which may be identical or different, represent a group chosen from alkyl groups, linear or branched, unsubstituted or substituted by at least one group chosen from alkoxy and carboxy groups; hydroxy and amino; and aryl groups unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; - R and R 'which may be the same or different represent a group selected from alkyl groups, linear or branched, unsubstituted or substituted by at least one group selected from alkoxy, carboxy, hydroxy and amino groups; aryl groups which are unsubstituted or substituted by at least one group selected from alkyl, alkoxy, carboxy, hydroxy and amino groups; Q and Q ', which may be identical or different, represent a group of formula: - (CH2) 1-,   - (CH2) m -CH = CH- (CH2) n-, - (CH2) mC = C- (CH2) n-, - (CH2) p- [O- (CH2) q] r-, - (CH2) p- [S- (CH2) q] r-, - (CH2) p- [O-R5-O- (CH2) q] r-, or - (CH2) p- [N (R6) - (CH2) q] r-   wherein R5 is phenylene or a divalent group derived from a heterocyclic ring, R6 is H or alkyl, and 1, m, n, p, q and r are integers such that 3 <1 <16 3 <q <16 1 <m <16 1 <n <16 1 <r <16 3 <p <16 to extract 1 '(the) actinide (s) in said immiscible phase. 11. The method of claim 10, characterized in that the immiscible phase is an organic liquid phase consisting of an organic solvent containing   in solution 1 '(the) phosphine oxide (s).   12. Process according to claim 11, characterized in that the organic solvent is a nitrophenylalkyl ether. 13. Process according to any one of   Claims 10 to 12, characterized in that one   recovering 1 '(the) actinides (s) extracted (s) in the immiscible phase by bringing it into contact with a   aqueous stripping solution having a pH of 1 to 7.   14. The method of claim 10, characterized in that the immiscible phase is constituted by a liquid membrane comprising 1 '(the) oxide (s) of phosphine (s), one of the faces of the membrane being in contact with the aqueous solution containing the actinides and the other side of the membrane being in   contact with an aqueous stripping solution.   15. Process according to any one of   claims 13 and 14, characterized in that the   aqueous stripping solution is an aqueous solution of oxalic acid, citric acid or a salt of these acids.   16. The method of claim 14, characterized in that the liquid membrane is a supported liquid membrane consisting of a microporous membrane whose pores are filled with dioxide (s) of diphosphine (s) in solution in an organic solvent immiscible with the water. 17. The method of claim 16, characterized in that the organic solvent is a nitrophenylalkyl ether. 18. Process according to any one of   Claims 10 to 17, characterized in that the   Diphosphine dioxide is 1,4-bis (3diphenylphosphinopropoxy) benzene dioxide or a   diphosphine according to claim 2.   19. Process according to any one of   Claims 10 to 18, characterized in that the   actinides are selected from plutonium and neptunium.