WO1995017409A1 - Diphosphine dioxides for removing actinides and phosphonium disalts for preparing same - Google Patents

Abstract

Diphosphine dioxides for removing actinides such as Pu, Am and Np from aqueous effluents and fission product concentrates from waste nuclear fuel reprocessing plants. The diphosphine dioxides have one of the following formulae (I) and (II), wherein R?1, R2, R3, R4¿, R and R' are optionally substituted aryl or alkyl groups, and Q and Q' are hydrocarbon chains optionally comprising oxygen, sulphur or nitrogen atoms.

Description

 DIPHOSPHIN DIOXIDES FOR USE IN THE EXTRACTION OF ACTINIDES AND PHOSPHONIUM DISSELS FOR THEIR PREPARATION

The present invention relates to dioxyαes αe diphosphines which can be used in particular for the extraction of actinides.

More specifically, it relates to diphosphine dioxides making it possible to selectively extract actinides from aqueous saline effluents, concentrates of fission products and solutions from plants for the reprocessing of spent nuclear fuels.

It is known that macrocyclic poly heteroatomic compounds constitute a very interesting class of ligands because they have complexing properties with respect to transition metals.

Among these macrocyclic compounds, the compounds with stable P-C bonds should exhibit new complexing properties. Also, work has been done to synthesize such compounds, in particular in the form of polyoxygenated diphosphorus macrocycles, as described by Cristau et al in Nouveau Journal de Chimie, vol. 8, n ° 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, n ° 12, 1974, p. 1748-1752. Polyoxygenated or polysulfurized macrocyclic diphosphorus compounds are also described by Markl et al in Tetrahedron Letters, vol 33, n ° 25, 1992, p. 3621-3624 or by Bader and Lmdner, 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 dioxins to diphosphines which are particularly suitable for the extraction of actinides from aqueous effluents, generally acidic, with high salinity and from fission product concentrates originating from nuclear fuel reprocessing installations. worn out.

According to the invention, the dioxides of diphosphines correspond to one of the following formulas:

dans lesquelles :

in which :

R ¹ , R ² , R ³ and R ⁴ 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 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 chosen from alkyl groups, linear or branched, unsubstituted or substituted by at least one group chosen from carboxy, alkoxy, hydroxy and amino groups; aryl groups unsubstituted or substituted by at least one group chosen from alkyl, alkoxy, carboxy, hydroxy and amino groups; Q and Q 'which may be the same or different, represent a group of formula:

- ⁽ CH ₂ ⁾ p- [0- ⁽ CH ₂ ⁾ q] r- / - (CH ₂ ) p- [S- (CH ₂ ) _q _ _r -,

- (CH ₂ ) _p - [0-R ⁵ -0- (CH ₂ ) _q ] _r -, or - (CH ₂ ) _p - [N (R ⁶ ) - (CH ₂ ) _q } _r -

in which R ⁵ represents a phenylene group or a bivalent group derived from a heterocyclic ring, R ⁶ represents H or an alkyl group and 1, m, n, p, q and r are integers such that

3 <p <16 3 <q <16

1 <r <16 provided that

(CH₂)₃- lorsque R¹, R², R³ et R⁴ sont tous des groupes phényle,1) in formula I, Q does not represent (CH ₂ )

(CH ₂ ) ₃ - when R ¹ , R ² , R ³ and R ⁴ are all phenyl groups,

2) in formula I, Q does not represent (CH ₂ ) _p - [0 (CH ₂ ) _q ] _r or [CH ₂ ) _p - [S (CH _2q ] _r when one of the

R ¹ , R ² , R ³ and R ⁴ is an alkyl group substituted by a hydroxy or alkoxy group, and

3) in formula II, Q and Q 'do not both represent (CH ₂ ) 3-0- (CH ₂ ) 3- or (CH ₂ ) 3 ~ 0— ^ O —0- (CH ₂ ) 3 ~ when R and R 'are both phenyl groups. The phosphine oxides described above are particularly interesting because they make it possible to extract more than 90% of the plutonium present at very low concentrations in aqueous effluents.

They therefore have performances equivalent to those of CMPO (octyl (phenyl) oxide -N, N'-diiso- butylcaroamoyl ethylpnospnine) which is the product currently used for this extraction.

In the formulas given above, the alkyl groups which can be used for R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R and R 'can be linear or branched groups, generally having from 1 to 16 carbon atoms, and preferably from 4 to 12 carbon atoms.

These alkyl groups may be substituted by one or more groups chosen from alkoxy, carboxy, hydroxy and amino groups, the alkoxy groups generally having from 1 to 12 carbon atoms.

The aryl groups capable of being used for R ¹ , R ² , R ³ , R ⁴ , R and R ′ may contain one or more aromatic rings, and may be substituted by one or more groups chosen from alkyl, alkoxy, carboxy, hydroxy and amino such as those described above.

As examples of aryl groups which may be used, mention may be made of phenyl and benzyl groups.

For Rg, the phenylene group can be the group

1, 2-phenylene, 1, 3-phenylene or 1, -phenylene; when

Rg is a group derived from a heteroatomic nucleus, this nucleus can be for example furan, thiophene, quinoline, pyridine and their derivatives.

formules (I) et (II) données ci-dessus, Q et Q' peuvent être divers chaînons hydrocarbones comportant éventuellement une double ou triple liaison, un ou plusieurs atomes d'oxygène et/ou de soufre, et des noyaux aromatiques. De préférence, Q et/ou Q' comportent des atomes d'oxygène et répondent par exemple aux formules suivantes :When R ^ is derived from a heteroatomic nucleus, a nucleus derived from pyridme is preferably used, for example the pyridine diyl group of *

formulas (I) and (II) given above, Q and Q ′ can be various hydrocarbon links optionally comprising a double or triple bond, one or more oxygen and / or sulfur atoms, and aromatic rings. Preferably, Q and / or Q ′ have oxygen atoms and correspond for example to the following formulas:

- (CH ₂ ⁾ 3-0- (CH ₂ ) 3- and

- (CH ₂ ) 3-O — Ç ^ -0- (CH ₂ ) ₂ -

The diphosphine dioxides of formula (I) can be prepared by a conventional process from the corresponding phosphonium disels, by subjecting the basic phosphonium disel of formula:

wherein R ¹ , R ² , R ³ , R ⁴ and Q have the meanings given above, R ⁷ and R ^ are benzyl or phenyl groups and X is a halogen atom.

The diphosphine dioxides of formula (II) can also be prepared by a conventional method from the corresponding phosphonium disels, by subjecting the basic phosphonium disel of formula:

dans laquelle R, R', Q et Q' ont les significations données ci-dessus, R⁷ et R⁸ sont des groupes benzyle ou phényle, et X est un atome d'halogène.

wherein R, R ', Q and Q' have the meanings given above, R ⁷ and R ⁸ are benzyl or phenyl groups, and X is a halogen atom.

A subject of the invention is also the phosphonium disels corresponding to formulas (III) and (IV) given above. In these phosphonium disels, X is preferably a bromine atom or an iodine atom.

The phosphonium disels of formula (III) can be prepared from the dihalides of formula QX ₂ by reaction of these with the corresponding phosphines of formula PR ¹ R ² R ⁷ and PR ³ R ⁴ R ⁸ as described by Cristau et al, in the New Journal of Chemistry, vol 8, n ° 3, 1984, p. 192. These disels of formula (III) can also be prepared by reaction of the diphosphines of formula PR ¹ R ⁷ -Q-PR ³ R ⁸ with the alkyl halides R ² X and R ⁴ X.

The phosphonium disels of formula (IV) can be prepared by the process described by Cristau et al in the Nouveau Journal de Chimie, vol 8, n ° 3, 1984, p. 191 to 199, by coupling between a biphosphine of formula RR ⁷ PQ-PR'R ⁸ with a dihalogen derivative Q'X ₂ .

Another subject of the invention is a process for the separation of actinides present in an aqueous solution resulting from the reprocessing of spent nuclear fuel, which consists in bringing this solution into contact with an immiscible phase comprising at least one diphosphine dioxide corresponding to one following formulas:

dans lesquelles : - R¹, R², R³ et R⁴ qui peuvent être identiques ou différents, représentent un groupe choisi parmi les groupes alkyle, linéaires ou ramifiés, non substitués ou substitués par au moins un groupe choisi parmi les groupes alcoxy, carboxy, hydroxy et amino ; et les groupes aryle non substitués ou substitués par au moins un groupe choisi parmi les groupes alkyle, alcoxy, carboxy, hydroxy et amino ;

in which: - R ¹ , R ² , R ³ and R ⁴ 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 groups, 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 ¹ which may be the same or different represent a group chosen from alkyl groups, linear or branched, unsubstituted or substituted by at least one group chosen from alkoxy, carboxy, hydroxy and amino groups; aryl groups unsubstituted or substituted by at least one group chosen from alkyl, alkoxy, carboxy, hydroxy and amino groups;

Q and Q 'which may be the same or different, represent a group of formula:

- (CH _2/1 -,

- (CH ₂ ) _m -CH = CH- (CH ₂ ) _n -, - (CH ₂ ) _p -CsC- (CH ₂ ) _n -,

- (CH ₂ ) _p - [0- (CH ₂ ) _q ] _r -,

- (CH ₂ ) _p - [S- (CH ₂ ) _q J _r _,

- (CH ₂ ) _p - [0-R ⁵ -0- (CH ₂ ) _q ] _r -, or

- (CH ₂ ) _p - [N (R ⁶ ) - (CH ₂ ) _q ] _r - in which R ^ represents a phenylene group or a bivalent group derived from a heterocyclic ring, R ⁶ represents H or an alkyl group and 1, m, n, p, q and r are whole numbers such that

3 <1 <16 3 <q <16 1 <m <16 1 <n <16 1 <r <16

pour extraire les actinides dans la phase immiscible.3 <p <16 provided that in formula (I), R ¹ is different from R ² or R ³ is different from R ⁴ when Q represents

to extract actinides in the immiscible phase.

According to a first embodiment of the process of the invention, the immiscible phase is an organic liquid phase consisting of an organic solvent containing the phosphine oxide (s) in solution.

The organic solvents which can be used are in particular ethers and alcohols. The ethers can be nitrophenylalkyl ethers such as nitrophenylhexyl ether and nitrophenyloctyl ether. As an example of alcohol which can be used, there may be mentioned isotridecanol.

The concentration of phosphine oxide in the organic phase is chosen so as to obtain the best extraction rate without the formation of a precipitate or of a third phase. It depends in particular on the solubility of the phosphine oxide in the organic solvent used. Generally, a phosphine oxide concentration of 10 ^-3 to 0.2 mol / l is used.

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 ^{- 1} to 4mol / l, which may also contain sodium in relatively high concentration, for example approximately

4 mol / 1 of Na ⁺ The actinides present in these solutions (aqueous effluents or concentrates of fission products) are for example Pu, Np, Am at concentrations generally lower than lg / 1. According to the invention, the contacting between the aqueous solution and the immiscible organic phase can be carried out in conventional equipment for liquid-liquid extraction such as mixer-settlers, exchange columns, pulsed columns etc.

Generally, the operation is carried out at atmospheric pressure and at ambient temperature.

After separation of the actinides in the immiscible phase, they can be recovered by bringing it into contact with an aqueous re-extraction solution having a pH ranging from 1 to 7.

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

According to a second embodiment of the method of the invention, the immiscible phase consists of a liquid membrane comprising the phosphine oxide (s), one of the faces of the membrane being contact with the aqueous solution containing the actinides and the other face being in contact with an aqueous re-extraction solution such as those described above. The liquid membrane can for example be a supported liquid membrane constituted by a microporous membrane playing the role of support, the pores of which are filled with diphosphine oxide (s) in solution in an organic solvent immiscible with water such as than the ethers and alcohols mentioned above.

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

To obtain good extraction with the supported liquid membranes, it is advantageous to use membranes having a small thickness, a large 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 with hollow fibers, which make it possible to treat large flow rates of fluid.

With such membranes, the aqueous re-extraction solution can be constituted as previously by a solution of citric acid, oxalic acid or a salt of these acids.

Other characteristics 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 appended figure schematically represents an actinide extraction device using a supported liquid membrane. Example 1: Preparation of 4-oxa-1,7-heptamethylene dioxide bis dodecylphenylphosphine dioxide (compound no.

1) of formula:

0 O

PP ^v O ^v PPh

1 I

12 "25 C | ₇ ri * .-;

C H72O3P2 M 686.99 a) Preparation of 4-oxa-1,7,7-heptamethylene bis dodecyldiphenylphosphonium dibromide (compound No. 2) of formula:

^c 54 ^H 82 ^Br 2 ^OP 2 '^{"M =} 969.02

This preparation corresponds to the following reaction scheme:

(compound n ° 2)

It is carried out under an atmosphere of pure and dry nitrogen.

10.7 ml (45 mmol) of 1-bromododecane and 7.0 g (14.88 mmol) of 4-oxa-1,7-heptamethylene bis diphenylphosphine in 80 ml of anhydrous dimethylformamide are introduced into a 250 ml two-necked flask fitted with a condenser. It is brought to 150 ° C. for 20 hours. Precipitated in ether and obtained (after drying under

0.1 mm Hg / P ₂ 05/4 h) 13.80 g of white gum (14.24 mmol) which does not recrystallize from CHCl 3 / ethyl acetate

(AcOEt). An ion exchange is carried out using 1.10 g (1.13 mmol) of gum and 1.46 g of NaBPh4. 1.60 g (l, llmmol) of white powder are obtained (after drying under p = 0, lmιuHg / t = 80 ^o C / P ₂ O ₅ / 24h). The yield is 96%. Identification

F = 270 ° C (ditetraphenylborate salt) RMNIJP of dibrominated salt (200 MHz; CDC1 ₃ ) δ26, 64 (s) I_R (KBr of ditetraphenylborate salt)

465 ff - 480 ff - 605 F - 615 m - 625 ff - 705 FF - 740 F - 745 F - 845 f - 1035 f - 1065 f - 1140 f - 1150 f - 1180 ff - 1220 ff - 1265 ff -1315ff- 1360 f - 1380 f - 1420 F - 1475 F - 1580 m - 1670 m - 3000 m - 3060 m. b) Preparation of 4-oxa-1,7,7-heptamethylene bis dodecylphenylphosphine dioxide.

This preparation corresponds to the following reaction scheme:

(compound # 2) (compound # 1)

5.2g (130mmol) of NaOH in 25ml of water, 12.16g (12.54mmol) of 4-oxa-l, 7-heptamethylene bis dodecyldiphenylphosphonium dibromide are introduced into a 250 ml two-necked flask fitted with a condenser. compound n ° 2) obtained previously and 80ml of benzene. The mixture is brought to reflux (71 ° C.) for 16 h, then decanted and extracted with chloroform; the organic phases are joined, washed with water, dried over Na ₂ S0, then the solvent is removed on an evaporator rotary. A white solid is obtained which is recrystallized from benzene / hexane.

5.40 g (7.86 mmol) of white powder are obtained (after drying under p = 0.4 mm Hg / P ₂ θ5 / t = 40 ° C / 24h).

The yield is 63%. Identification White solid F = 70 ° C (benzene / hexane). RMNIH (200MHz; CDC1 ₃ ; C = 0.08 M) δ 0.87 (t; 6H; 2 CH3; J = 6Hz); 1.21 (s; 36 H; 18 internal CH ₂ ); 1.45 - 2.1 (m; 16 H; 4 CH ₂ -P = 0 and 4 CH ₂ internal); 3.2 - 3.4 (m; 4 H; 2 CH ₂ -0); 7.64

(s; 6 H; meta and para); 7.6 -7, m 4 H; ortho). RMNIIP (81 MHz; CDCI3; C = 0.08 M) δ 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 f - 1470 F - 1480 f - 1590 ff - 1900 ff - 1970 ff - 2800 f - 2850 FF - 2920 FF - 3060 f. Centesimal analysis

FOB mass (matrix used alcohol

1-neutrobenzyl (NOBA) (M + 2H) ⁺ = 688. 95/17409

1 4

Example 2: Preparation of 1,8-octamethylene bis dodecylphenylphosphine dioxide (compound No. 3) of formula:

10 ^c 44 ^H 7β ° 2 ^p 2; M = 699.04 a) Preparation of 1,8-octamethylene diodide bis dodecyldiphenylphosphonium diiodide (compound No. 4) of formula:

15

20

C56 ^H 86 ^I 2 ^p 2; M = 1075, 065

This preparation corresponds to the following reaction scheme:

(compound n ° 4)

30 It is carried out under an atmosphere of pure and dry nitrogen.

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 a 100 ml flask fitted with a condenser. in 50ml of anhydrous dimethylformamide. We bring to

140 ° C for 80h.

0,784g de solide jaune pâle.An ion exchange is carried out by successive washings with an aqueous solution of 12 mmol of Nal. Precipitate in ether and obtain (after drying under p = 0,

0.784 g of pale yellow solid.

The yield is 77%.

Identification of C -, gHg I_ P Pale yellow solid

F = 112 ° C

R NJH (250 MHz; CDC1 ₃ ; C = 0.3M) δ 0.74 (t; 6 H; 2 CH ₃ ; J = 7Hz); 0.95 - 1.25 (m; 36

H; 18 internal CH ₂ ); 1.40 (s; 16 H; 8 internal CH ₂ ); 3.1 (s; 8 H; 4 CH ₂ -P ⁺ ); 7.5-5.7 (m; 12 H; meta and para); 7.7-7.9 (m; 8 H; ortho).

1 P NMR (81 MHz; CDCI3; 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 FF - 2930 FF - 3010 f - 3060 f. b) Preparation of 1, 8-octamethylene dioxide bis dodecyl phenylphosphine.

This preparation corresponds to the following reaction scheme:

(compound # 4) (compound # 3) 0.22 g (5.62 mmol) of NaOH in 4 ml of water, 0.6037 g ((0.562 mmol) of 1, 8-octamethylene bis dodecyldiphenylphosphonium diiodide (0.22 g (5.62 mmol) of NaOH) are introduced into a 100 ml two-necked flask fitted with a condenser. compound n ° 4) obtained previously and 50 ml of benzene. The mixture is brought to reflux (75 ° C.) for 120 h then it is extended with water, decanted and extracted with chloroform; the organic phases are joined, washed with water. water, they are dried over Na ₂ S puis ₇ and then the solvent is removed on a rotary evaporator to obtain (after drying under p≈lmrn Hg / P ₂ θ5 / 24h) 0.3923 g of white solid.

The yield is 100%. Identification Solid white F = 57 ° C

RMNJH (250 MHz; CDCI3; C = 0.08 M) δ 0.86 (t; 6H; 2 CH3; J = 6.8 Hz); 1.1 - 1.4 and 1.4

- 1.7 (m; 52 H; 26 internal CH) 1.7 - 2.0 (m; 8 H; 4 CH ₂ -P = 0); 7.4 - 7.5 (m; 6 H meta and para); 7.5 - 7.8 (m; 4 H; ortho).

RMNJlP (80 MHz; CDCI3; C = 0.08 M) δ 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 F -

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

- 1590 ff - 1820 ff - 1900 ff - 1960 ff - 2860 FF - 2920 FF - 3060 ff - 3080 ff. Centesimal analysis (dried 6h / P θ5 / 0.4 mm Hg)

Masse : FAB (matrice utilisée ; NOBA) (M+H)⁺=699.

Mass: FAB (matrix used; NOBA) (M + H) ⁺ = 699.

Example 3: Preparation of 1,4-bis (3- dioxide phénylphosphinopropoxy dodecyl) benzene (Compound No. 5 ^e of the formula:

^C 48 76 ° 4 ^P 2 'M = 779.086 a) Preparation of 1,4-bis (3-dodecyldiphenylphosphoniopropoxy) benzene dibromide (compound No. 6) of formula:

C ₆₀ H ₈₆ Br ₂ O ₂ P ₂ ; M = 1155.109.

This preparation corresponds to the following diagram

C ₁₂ H25Br

(composé n^β 6)

(compound n ^β 6)

It is carried out under an atmosphere of pure and dry nitrogen.

0.47ml of 1-bromododecane (1.96mmol) and 0.5g of 1,4-bis (3-diphenylphosphinopropoxy) benzene are introduced into a 100ml bicol with a refrigerant. (0.69 mmol) in 50 ml of anhydrous dimethylformamide. The mixture is brought to 140 ° C. for 48 hours then precipitated in hexane and one obtains (after drying under p = lmm

Hg / P ₂ θ5 / 2h) 0.60g of pale yellow solid. The yield is 82%.

Identification

M = 56-57 ° C pale yellow solid

NMR JH (250 MHz; CDC1 ₃ ; C = 0.05 M) δ 0.82 (t; 6 H; 2 CH3; J = 6Hz); 1.15 (s broad;

32 H; 16 internal CH ₂ ); 1.47 (s; 8 H; 4 internal CH ₂ ); 3.16 (s; 4H; 2 CH ₂ -P ⁺ ); 3.41 (s,;

4 H; 2 CH ₂ -P ⁺ ); 4.02 (broad s; 4 H; 2 CH ₂ 0); 6.66

(s; 4 H; H hydroquinoneic); 7.6-7.9 (m; 20 H; aromatic).

RMNJlP (81 MHz; CDCI3; C = 0.05 M)

Ô28.6 (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 FF - 2930 FF - 3010 f - 3060 f. b) Preparation of 1,4-bis (3-dodecyl phenylphosphinopropoxy dioxide) benzene.

This preparation corresponds to the following reaction scheme:

⁽ compound n ° 6 ⁾ (compound n ° 5) 0.19 g of NaOH (4.68 mmol) in 1 ml of water, 0.54 g of 1.4 bis dibromide (3-dodecylbiphenyl phosphoniopropoxy) benzene (0.68 mmol) are introduced into a 100 ml flask fitted with a condenser ) (compound n ° 6) obtained previously and 40ml of benzene. The mixture is brought to reflux (75 ° C.) for 86 h then it is extended with water, decanted and extracted with chloroform; the organic phases are joined, washed with water, dried over Na Sθ, then the solvent is removed on a rotary evaporator. 0.29 g of white solid is obtained which after recrystallization (benzene / hexane) provides 0.17 g of white compound (dried at p = 0.1 mm Hg / P ₂ θ5 / 6h). The yield is 47%. Solid white identification

F = 67-68 ° C (benzene / hexane)

RMNJH (200 MHz; CDC1 ₃ ; C = 0.07 M) δ 0.87 (t; 6 H; 2 CH ₃ ; H = 6 Hz); 1.1 - 2.25 (m;

52 H; 26 CH ₂ ); 3.89 (t; 4 H; 2 CH ₂ 0; J = 4.6 Hz); 6.72 pp (s; 4 H; H hydroquinone); 7.26 - 7.5 (m; 6 H; meta and para); 7, 6 - 7, 8 (m; 4 H; H ortho). 1 H NMR (81 MHz; CDCI3; C = 0.07 M) δ 41.0 (s). 1 NMR c (50.3 MHz; CDCI3; C = 0.24 M) δ 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 - 30.66 - 30, 77 - 30.94 - 31.74 (m; CH2); 68.13 (d; CH 0; J = 13.9 Hz); 115.21 (s; C hydroquinone ortho); 128.51 (d; meta; J = 11.1 Hz); 130.27 (d; ortho; J = 8.8 Hz); 131.41 (d; para; J = 2.7 Hz); 132.19 (d; ipso; J = 92.2 Hz); 152.76 (s; C hydroquinone ipso). Centesimal analysis (dried h / P ₂ θ5 / mm Hg)

IE mass

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 F - 2921 FF - 2954 FF. Example 4 Preparation of 5, 13-5, 13-dioxide-didodecyl-1, 9-dioxa-5, 13-diphosphacyclohexadecane

(compounds 7 and 8 n ^e) of formula:

C3 ₄ H ₇₄ 0 ₄ P; M = 632, 936 a) Preparation of the diiodide of 5, 13-didodecyl-5, 13-diphenyl-1, 9-dioxa-5, 13-diphosphonia cyclohexadecane

(compound n ° 9)

C4 ₈ H ₈ I ₂ 0 ₂ P ₂ ; M = 1008, 959

This preparation corresponds to the following reaction scheme:

⁽ compound n ° 9)

It is carried out under an atmosphere of pure and dry nitrogen.

Is introduced into a 250 ml 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 in 200 ml of anhydrous chloroform; in a first three-necked flask of 11, 400 ml of anhydrous chloroform are introduced and in a second three-necked flask of 11,400 ml of dimethylformamide and 100 ml of anhydrous chloroform. The second tricolor is brought to 135 ° C. The chloroform circulates from the first three-neck to the second three-neck using a peristaltic pump (200ml / h) and from the second three-neck to the first three-neck by distillation. When the distillation is well established, the slow addition of the reagents from the ampoule to the first three-necked flask is started (3 hrs) and the cycle is continued for 48 hrs. The reaction mixture turns brown. The pump is stopped and the CHCI3 is allowed to distill, then the second three-necked flask is cooled, it is concentrated on a rotary evaporator, the brown paste obtained is taken up in 50ml of CHCI3 and washed with 3 times four Nal equivalents. The mixture is precipitated in hexane and 3.12 g of brown precipitate are obtained. The precipitate obtained is recrystallized from CHCl3 / AcOEt then slow diffusion of hexane and provides (after drying under p = lmm

Hg / P ₂ θ5 / 4h) 2.10g of beige powder. The yield is

57%. Identification

F = 172-174 ° C (CHCl ₃ / AcOEt / hexane - Leitz)

RMNJH (250 MHz; CDC1 ₃ ; C = 0.8M) δ 0.86 (t; 6 H; 2 CH3; J = 6.5 Hz); 1.23 (s) and 1.4 -

2.15 (m; 48 H; 24 internal CH ₂ ); 2.65 - 3.85 (m; 20 H; 4 CH ₂ 0 and 6 CH ₂ -P ⁺ ); 7.65 - 7.75 (m; 6H, meta and para); 7.9 - 8.05 (m; 4 H; ortho).

RMN1JP (81 MHz; CDCI3; C = 0.06M) δ 32.32 (s) and 32.46 (s) (same integration - presence of the two cis and trans isomers). NMRllc (50.3 MHz; J mod; CDCI3; C = 0.09M)

13.90 (s, CH3); 69.15 (d; J = 10 Hz; CH2-0); 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 -

30.15 to 30.22 - 30.45 to 30.53 (m; internal and CH ₂ CH ₂ - P ⁺ for each cis and trans isomer); 117.33 (d; J = 79, l

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: FOB (Noba):

[M- (I ")] ⁺ = 881; m / z = 138

^ R (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 = 0.1 mm

Hg / t = 80 ° C / P ₂ O ₅ / 24h) 23

b) Preparation of 5, 13-dioxide of 5, 13-didodecyl-1, 9-dioxa-5, 13-diphosphacyclohexadecane.

This preparation corresponds to the following reaction scheme:

Ph NaOH C | ₂ -_hH ₂ ? S <T ^c 'P * h ^H _2I ^• C ₁₂ H ₂ d - P = 0 0 = - CUHJJ

EtOH-H ₂ 0

72hi80 ° C ^

(compound n ° 9) (compounds 7 and 8)

0.59 g (14.7 mmol) of NaOH in 2.9 ml of water, 1.48 g (1.47 mmol) of 5, 13-didodecyl-5 diiodide are introduced into a 25 ml two-necked flask fitted with a condenser. 13-diphenyl-1, 9-dioxa-5, 13-diphosphoniacyclohexadecane (compound n ° 9) obtained previously and 15 ml of ethanol. The mixture is brought to reflux (80 ° C.) for 72 hours. The mixture is extended with water and the ethanol / water azeotrope is removed on a rotary evaporator. Is extended to water and chloroform, decanted and extracted with chloroform; the organic phases are joined, washed with water until neutral, dried over Na ₂ Sθ4, then the solvent is removed on a rotary evaporator. 0.92g of beige-brown solid is obtained (after drying under p = 1 mmHg / P ₂ 05 / 4h). ³¹ P NMR analysis shows the unique presence of the two stereoisomers cis and trans. The yield is 92%. Chro atography on Lobar (eluent AcOEt / MeOH 85/15) to separate the two isomers and then recrystallize from benzene / hexane.

The two isomers have the following characteristics: A. Alpha isomer of formula:

(compound n ° 7)

C ₃₄ H74θ4P; M ≈ 632.936 Identification of the alp isomer * ha

Solid white

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

Rf = 0.1 (Si0 ₂ - AcOEt / MeOH 80/20-I ₂ )

RMNJH (250 MHz; CDCI3; C = 0.06 M) δ 0.87 (t; 6H; 2 CH ₃ ; J = 6.5 Hz) and 1.5 - 1.7 (m) and 1.75 - 1.9 (m) chain, 4 CH ₂ cycle and 6 CH ₂ -P = 0);

8 H; 4 CH ₂ -0).

11p NMR (81 MHz; CDCI3; C = 0.13 M) Ô 50.02 (s)

1 C NMR (50.3 MHz; CDCI3; C = 0.09 M) δ 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 to 30.92 - 31.19 to 31.78 (m, CH ₂ CH ₂ and internal - P = 0); 70.29 (d; J = 12.6 Hz; CH ₂ 0).

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 1435 f - 1462 m - 2775 f - 2855 FF - 2915 FF. Centesimal analysis (dried under p 0.02 mm

Hg / t = 60 ° C / 48h / P ₂ O ₅ .

Mass El

M = 632 - m / z = 317

B. Beta isomer of formula

(compound n ° 8)

^C 34 ^H 74 ° 4 ^P 2 ' ^{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 ) RMNJH (250 MHz; CDC1 ₃ ; C = 0.06 M) δ 0.87 (t; 6H; 2 CH ₃ ; J = 6.5 Hz); 1.24 (s wide) and 1.5 - 1.7 (m) and 1.75 - 1.9 (m) (60 H; 20 CH ₂ chain, 4 CH ₂ cycle and 6 CH ₂ -P = 0 ) 3.4 - 3.5 (m;

8 H; 4 CH ₂ -0).

RMNIJP (80 MHz, CDCI3, C = 0.13 M) δ 49.61 (s)

12 C NMR (50.3 MHz; CDCI3; C = 0.09 M) δ 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 to 30.79 - 30.92 - 31.19 to 31.76 (m, CH ₂ CH ₂ internal and -P = 0); 70.29 (d; J = 12.2 Hz; CH ₂ -0). IR (KBr)

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 F - 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 at p = 0.02 mm Hg / t = 60 ° C / 48h / P ₂ O ₅ )

Mass El

M = 632 - m / z = 317. Example 5 Preparation of 4-oxa-1,7-heptamethylene bis 2 '-ethoxyethyl) phenylphosphine dioxide

[compound n ° 10) of formula:

C ₂ 6 ^H 40 ° 5 ^P 2 ^{; M =} 49'553 a) Preparation of 4-oxa-1,7,7-heptamethylene di (2'-methoxyethyl) diphenylphosphonium diiodide (compound n ° 11) of formula:

C38H46l2θ3 ^p 2 M = 842.520 This preparation corresponds to the following reaction scheme:

DMF / N;

⁽ compound n ° 11)

It is carried out under an atmosphere of pure and dry nitrogen.

0.74 ml (7.66 mmol) of 2-bromoethyl methyl ether and 1.20 g (2.56 mmol) of 4-oxa-1,7-heptamethylene bis diphenylphosphine are introduced into a 100 ml two-necked flask fitted with a condenser anhydrous dimethylformamide. It is brought to 100 ° C. for 70 h then an ion exchange is carried out by successive washing with an aqueous solution of 25.5 mmol of Nal. 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 / P ₂ 05 / 24h, there is 2.3 g of paste.

The reaction is quantitative. Identification brown paste

RMN2_LP (81 MHz; CDC1 ₃ ; C = 0.07) δ 30.07 (s)

RMNJH (200 MHz; CDCI3; C = 0.07) δ 1.14 ppm (t; 4 H; ₂ internal CH ₂ ; J = 7 Hz); 1.65-1.85 (m; 4 H; 2 H ₂ 0); 3.01 (s; 6H; 2 CH ₃ - 0); 3.3-3.65 (m; 16H; 4 CH ₂ -0 and 4 CH ₂ -P ⁺ ); 7.55- 7.75 (m; 12 H; meta and para); 7.85-8.0 (m; 8 H; ortho). b) Preparation of 4-oxa-1,7-heptamethylene bis (2 '-ethoxyethyl) phenylphosphine dioxide.

This preparation corresponds to the following reaction scheme:

^{(O p} posed ^"• u _{(composed. No C}

0.89 g (22.3 mmol) of NaOH in 4.5 ml of water, 1.88 g (2.23 mmol) of 4-oxa-1, 7- diiodide are introduced into a 50 ml flask fitted with a condenser heptamethylene bis (2 '-methoxyethyl) diphenylphosphonium (compound No. 11) obtained previously and 30 ml of ethanol. The mixture is brought to reflux (79 ° C.) for 4 days then it is extended with water, the azeotrope is removed on a rotary evaporator and then extracted with chloroform; the organic phases are joined, washed with water, dried over a ₂ S0, then the solvent is removed on a rotary evaporator. 1.08 g of yellow oil are obtained. A ^ -P NMR study shows the presence of the product at about 58% as well as that of another phosphine oxide.

The yield is 58%. Chromatography on lobar (eluting AcOEt / MeOH 80/20 ⁾ and one obtains inter alia a white solid (after drying under p = lmm Hg / P ₂ θ5 / t = 40 ° C / 24h). Identification Solid blanc F = 73-74 ° C (Leitz) RMNJH (200 MHz; CDC1 ₃ ; C = 0.12 M) δ 1.11 (t, 3 H; CH ₃ ; J = 7 Hz); 1.12 (t; 3 H; CH ₃ ; J = 7 Hz); 1.6 - 2.4 (m; 12 H; 4 CH ₂ -P = 0 and ₂ internal CH ₂ ); 3.25 - 3.80 (m; 12 H; 6 CH ₂ -0); 7.4

- 7.55 (m; 6 H; meta and para) 7, 6 - 7.75 (m 4 H ortho).

RMNUP (81 MHz; CDCI3; C = 0.08 M) δ 41, 15 (s).

RMNJlc (50.3 MHz; CDCI3; 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 -0; J = 1.9

Hz); 66.05 (s; Me-CH ₂ -0); 70.29 (d; CH ₂ -0; J =

14.8 Hz); 128.42 (d; meta; J = 11.3 Hz); 130.12 (d

; ortho; J = 9.0 Hz); 131.44 (d; para; 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 F - 2928 m - 2946 m - 2976 m - 3060 ff - 3080 ff.

Centesimal analysis

Mas se :

Mass :

FAB (matrix used: NOBA)

(M + H) ⁺ = 495.

IE

M ⁺ = 494 - m / z = 255.

Example 6: Preparation of 4-oxa-1,7-heptamethylene (2-ethoxyethyl) phenylphosphine diphenylphosphine dioxide (compound No. 12) of formula:

28 ^H 36 ° 4 ^P 2 ' ^{* M =} 498 ^ 4

This preparation corresponds to the following reaction scheme:

(compound n ° 11)

0.89 g (22.3 mmol) of NaOH in 4.5 ml of water are introduced into a 50 ml two-necked flask fitted with a condenser.

1.88g (2.23mmol) 4-oxa-1,7-heptamethylene di (2-methoxyethyl) diphenylphosphonium diiodide

(compound No. 11) obtained in Example 5a) and 30 ml of ethanol. It is brought to reflux (79 ° C.) for 4 days then it is extended with water, the azeotrope is removed on rotary evaporator and extraction with chloroform; the organic phases are joined, washed with water, dried over a ₂ Sθ4, then the solvent is removed on a rotary evaporator. 1.08 g of yellow oil are obtained. A ³¹ P NMR study shows the presence of the product at around 38% as well as that of another phosphine oxide.

The yield is 38%.

Chromatography on lobar (eluting AcOEt / MeOH 80/20) and one obtains inter alia a yellowish paste which tends to crystallize (after drying under p = lmm

Hg / P ₂ O ₅ / t = 40 ° C / 24h).

Identification

Yellowish paste RMNJLH (200 MHz; CDC1 ₃ ; C = 0.12 M) δ 1.07 (t, 3 H; CH ₃ ; J = 7 Hz); 1.55 - 2.4 (m;

10 H; 3 CH ₂ -P = 0 and 2 CH ₂ internal); 2.51 (s; 1H;

0.5 H ₂ 0); 3.25 - 3.80 (m; 8 H; 4 CH ₂ -0); 7.35 -

(81 MHz ; CDCI3 ; C=0, 08 M) δ 33,31 (s) ; 39,45 (s) environ la même intégration.7.55 (m; 9 H; meta and para); 7.6 - 7.75 (m; 6 H; ortho).

(81 MHz; CDCI3; C = 0.08 M) δ 33.31 (s); 39.45 (s) approximately the same integration.

1 NMR c (50.3 MHz; CDCI3; C = 0.29 M) δ 14.86 (s; CH3); 21.65 (d; internal CH2; J = 3.9 Hz); 21.77 (d; internal CH ₂ ; 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 -0; J = 2.1 Hz); 66.08 (s; Me-CH ₂ -0); 70.20 (d;

CH -0; J = 14.6 Hz); 70.29 (d; CH -0; 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; para; 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 we differentiated the 2 C ipso:

132.73 (d; ipso; J = 98.4 Hz); 132.74 (d; ipso; J

= 98.5 Hz)

I_R (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. Weight: El

M = 498 - m / z = 258.

Centesimal analysis: M + 1.3H ₂ 0

Example 7: Preparation of 1,4-bis (3- (3'-methoxypropyl) phenylphosphinopropoxy)] benzene (compound No. 13) of formula:

^c 32 ^H 44 ° 6 ^p 2 '^{' M = 586} ' ⁶⁴⁴ a) Preparation of 1,4-bis [3- (3' methoxypropyl) diphenylphosphoniopropoxy] benzene diiodide

(compound n ° 14) of formula:

^C 44 ^H 54 ^I 2 ° 4 ^P 2> ^M = 962.669

This preparation corresponds to the following reaction scheme:

(compound n ° 14)

It is carried out under an atmosphere of pure and dry nitrogen.

0.24 g of l-bromo-3-methoxypropane (1.56 mmol) and 0.29 g of 1,4-bis (3-diphenylphosphinopropoxy) benzene (5, 15.10 ^~) are introduced into a 100 ml two-necked flask fitted with a condenser. ⁴ mol) in 70 ml of anhydrous dimethylformamide. The mixture is brought to 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 Nal. It is precipitated in ether and we obtain (after drying under p = 1 mm Hg / P ₂ θ5 / 4h) 0.51g of hygroscopic crude containing 5% ether. The gross yield is 98%.

The phosphonium salt will be used as it is for the following. Identification 1 H NMR hygroscopic solid (200 MHz; CDC1 ₃ ; C = 0.7 M) δ 1.18 (t; 4 H; CH ₃ ether; J = 7 Hz); 1.75 - 2.10 (m; 8 H; 4 CH ₂ internal); 3.10 - 3.80 (m; 20.6 H; 2 O-CH3, 2 CH ₂ -0, 4 CH ₂ -P ⁺ and CH ₂ ether); 4.0 - 4.20 (m; 4 H; 2 CH ₂ -OPh); 6.60 - 6.80 (m; 4 H; H hydroqumonics); 7.50 - 8.0 (m; 20 H aromatic). RMNIJP (81 MHz; CDCI3; C = 0.7 M) δ 29.05 (s; majority); 29.06 (s)

1 C NMR (50.3 MHz; CDCI3; C = 0.7 M; J modulated) 18.30 (d; internal CH ₂ ; J = 2.7 Hz); 19.35 (s; internal CH ₂ ); 22.47 (d; CH ₂ -P ⁺ ; J = 20.5 Hz); 22.16 (d; CH -P ⁺ ; J = 21.1 Hz); 58.60 (s; O-CH3); 66.76 (d; CH ₂ -0; J = 16.3 Hz); 70.66 (d; CH -0; J

= 15.1 Hz); 115.46 (s; hydroqumonic CH); 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; C hydroqumonics). The Cs of ethyl ether are observed as well as some secondary peaks at the level of the aromatic Cs. Mass: FAB (NBA [M- (I ^" )] ⁺ = 835 b) Preparation of 1,4-bis (3- (3'-methoxy-propyl) phenylphosphinopropoxy) benzene dioxide. This preparation corresponds to the following reaction scheme:

Elle est effectuée sous atmosphère d'azote pur et sec.

It is carried out under an atmosphere of pure and dry nitrogen.

In a 100 ml bicol fitted with a condenser, 0.20 g of NaOH (4.7 mmol) are introduced into 2 ml of water and

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

(4.44.10 ^-4 mol- P _m = 95%) (compound No. 14) obtained previously in 25 ml of benzene. The mixture is brought to reflux (70 ° C.) for 24 hours, decanted, the organic phase is washed with water until neutral, dried over Na ₂ S04 and obtained (after drying under p = lmm Hg / P ₂ θ5 / 4h) 0.27g of oil which tends to crystallize. The reaction is quantitative. Identification

1 H NMR (200 MHz; CDC1 ₃ ; C = 0.1 M) δ 1.60 - 2.30 (m; 16 H; 4 internal CH and 4 CH ₂ - P = 0); 3.00 - 3.50 (m; 10 H; 2 O-CH3 and 2 CH ₂ -0); 3.70 - 4.00 (m; 4 H; 2 CH ₂ -0); 6.60 - 6.80 (m; 4 H; H hydroquinone); 7.40 - 7.60 (m; 6 H; para); 7.60 - 8.0 (m; 4 H; ortho). RMNIIP (81 MHz; CDCI3; C = 0.1 M) Ô 41, 18 (s). 1 NMR c (50.3 MHz; J modulated; CDCI3; C = 0.7 M) δ 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-CH3); 68.14 (d; CH ₂ -0; J = 13.9 Hz); 72.30 (d; CH ₂ -0; J = 14.2 Hz); 115.26 (s; hydroquinone CH); 128.60 (d; eta; 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-0 hydroquinone). _IR (KBr) 460 f - 487 m - 500 F - 515 F - 545 F - 690 F - 710 m - 720 F - 738 F - 752 F - 765 F - 798 f - 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 f - 1435 F - 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, -bis (3-diphenylphosphinopropoxy dioxide) benzene (compound No. 15) of formula:

C ₃ gH3 ₆ 0 ₄ P ₂ ; M = 594.63 a) Preparation of 1,4-bis (3-triphenylphosphoniopropoxy) benzene dibromide (compound No. 16) of formula:

^c 42 ^H 48 ^Br 2 ° 2 ^p 2 ^{M =} 806.615

This preparation corresponds to the following reaction scheme:

_{+ *} . / +

(compound n ° 16) It is carried out under an atmosphere of pure and dry nitrogen.

3.87 g of 1,4-bis (3-bromopropoxy) benzene (10.99 mmol), 7.87 g of triphenylphosphine (30 mmol) and 100 ml of anhydrous dimethylformamide are introduced into a 250 ml two-necked flask fitted with a condenser. It is brought to 140 ° C for 16h. It is concentrated on a rotary evaporator, it is taken up in a few ml of MeOH and precipitated from ether. A white solid is obtained which is recrystallized from CHCl3 (and a few drops of MeOH) / AcOEt.

8.03g of white crystals (9.96mmol) are obtained (after drying under 0.1mm Hg / P ₂ θ5 / 4h).

The yield is 90% Identification

F = 268 ° C (CHC1 ₃ (and a few drops of MeOH) / AcOEt) RMNJH (250 MHz; CD3OD; C = 0.07M) δ 2 - 2.2 (m; 4 H; ₂ internal CH ₂ ); 3.45 - 3.65 (m; 4H; 2 CH ₂ -P ⁺ ); 4.05 - 4.15 (m; 4 H; 2 CH ₂ 0); 6.8 (s; 4H; O-Ph-O); 7.65 - 7.90 ppm (m; 30 H; aromatic).

1 P NMR (81 MHz; CD3OD; C = 0.07M) δ 24.36 (s)

IR (KBr) (after drying under p = 0, lmm Hg / t = 80 ° C / P θ5 / 24h 435 f - 465 f - 500 F - 510 F - 538 F - 612 ff - 690 FF

- 720 FF - 745 FF - 822 m - 840 f - 915 ff - 940 ff - 995 m - 1040 F (stepped) - 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-diphenylphosphmopropoxy dioxide) benzene.

composé n° 16) (composé n° 15)This preparation corresponds to the following reaction scheme:

compound # 16) (compound # 15)

In a 250ml bicol fitted with a refrigerant, we

10 introduced 3.5 g of NaOH (87.6 mmol) into 17.5 ml of water, 7.38 g of 1,4-bis (3-triphenylphosphoniopropoxy) benzene dibromide (9,15ιτ_mol) (compound No. 16) obtained previously and 80ml of ethanol. The mixture is brought to reflux (78 ° C.) for 48 hours. We extend to the water, we

15 expels the azeotrope on a rotary evaporator, decanted, extracted with CHCl3; the organic phases are joined, washed with water, dried over Na ₂ S0 ₄ , then the solvent is removed on a rotary evaporator. A solid is obtained which is recrystallized from benzene (and

20 a few drops of CHCI3) / hexane.

4.48g of white powder are obtained (after drying under p = 0.5mm Hg / P ₂ θ5 / 24h).

The yield is 82%. Identification

25 Solid white.

F = 183 ° C (benzene / hexane)

RMNJH (200 MHz; CDCI3; C = 0.11 M) δ 1.9 - 2.2 (m; 4 H; ₂ internal CH ₂ ) 2.3 - 2.6 m;

4 H; 2 CH ₂ -P = 0); 3.94 (t; 4 H; 2 CH -0; J - ^• = 5, 8

30 Hz); 6.74 (s; 4H; O-Ph-O); 7.2 - 7.6 (m 12 H; meta and para); 7, 6 - 7, 8 (m; 8 H; H ortho). R NIJP (81 MHz; CDCI3; C = 0.11M) δ 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 F - 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)

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 is evaluated for extracting plutonium, neptunium and americium from an aqueous solution containing one of these elements.

The composition of the aqueous solution is as follows:

HNO3: lmol / 1 NaNθ3: 4mol / l pH: * 0 Pu: 0.6 mg / 1 Am: 0.02 mg / 1 Np: 200 mg / 1

In these examples, 3 ml of the aqueous solution are brought into contact with 3 ml of an organic solution consisting of nitrophenyloctylether containing 0.01 mol / l of the diphosphine dioxide used. The contacting is carried out in a 20 ml polypropylene tube which is subjected to stirring. After 1 hour of contacting, the two phases are allowed to settle and the activity of each phase is counted by liquid scintillation.

The distribution coefficient D is then determined which corresponds to the ratio of the activity of actinide in the organic phase to the activity of actinide in the aqueous phase. The percentage of actmide extracted in the organic phase is also determined by the relation:

100D% of actmide extracted =

1 + D

The extractants used as well as the results obtained for the extraction are given in Table 1 which follows.

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

In this table, the results obtained when using CMPO at a concentration of 0.01 mol / l in nitrophenylhexyl ether were also given for comparison.

In view of these results, it is noted that all the oxides tested extract more than 90% of the plutonium and also the neptunium with good yields. On the other hand, trivalent actinides such as americium are less extracted, which is not the case with CMPO. Thus, the diphosphine dioxides of the invention have an efficiency comparable to that of CMPO and they are more selective than CMPO with respect to trivalent actinides. Examples 18 to 24.

In these examples, the second embodiment of the method of the invention is used to extract neptunium and plutonium from aqueous solutions having the same compositions as those used in examples 9 to 17. In these examples, the device represents in the appended 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 μm

Membrane thickness: 0.025 mm.

The pores of this membrane are filled with an organic phase consisting of nitrophenylhexylether comprising 0.01 mol / 1 of diphosphine dioxide. The two compartments 3 and 5 are fitted with magnetic stirrers 9.

Compartment 3 contains 50 ml of the aqueous solution (NaN03_4 mol / 1, HNO3: 1 mol / 1 with Pu or Np) and compartment 5 contains 50 ml of an aqueous re-extraction solution consisting of an aqueous solution with

0.25 mol / 1 of sodium citrate.

The two solutions are subjected to stirring, and the initial activity of the solution in compartment 3 is then determined, then the activity of the aqueous solution for re-extracting compartment 5 by liquid α spectrometry, and the operation is continued for several days. We deduce the percentage of neptunium and plutonium recovered in the aqueous re-extraction solution after 24 h, as well as the maximum re-extracted. The phosphine oxides used, the permeability of the membrane to Np and to Pu, as well as the% after 24 h 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 re-extraction solution.

Table 1

Claims

1. Diphosphine dioxide corresponding to one of the following formulas:

in which : - R ¹ , R ² , R ³ and R ⁴ 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, carboxy, hydroxy groups 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 chosen from alkyl groups, linear or branched, unsubstituted or substituted by at least one group chosen from alkoxy, carboxy, hydroxy and amino groups; aryl groups unsubstituted or substituted by at least one group chosen from alkyl, alkoxy, carboxy, hydroxy and amino groups; - Q and Q 'which may be identical or different, represent a group of formula: - (CH ₂ ) p- [0- (CH ₂ ) q] _r -, - (CH ₂ ) p- [S- (CH ₂ ) q] r-, - (CH ₂ ) _p - [0-R ⁵ -0- (CH ₂ ) _q ] _r -, or - (CH ₂ ) _p - [N (R ⁶ ) - (CH ₂ ) _q ] _r - in which R ⁵ represents a phenylene group or a bivalent group derived from a heterocyclic ring, R ⁶ represents H or an alkyl group, and 1, m, n, p, q and r are whole numbers such that 3 <p <lβ 3 <p <16 3 <q <16 1 <r <16 provided that 1) in formula I, Q does not represent (CH ₂ ) ₃ -C ~ ^ —0- (CH ₂ ) ₃ - when R ¹ , R ² , R ³ and R ⁴ are all phenyl groups, 2) in formula I, Q does not represent (CH ₂ ) _p - [0 (CH ₂ ) _q ] _r or (CH ₂ ) _p - [S (CH ₂ ) _q ] _r , when one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group substituted by a hydroxy or alkoxy group, and 3) in formula II, Q and Q ¹ do not both represent (CH ₂ ) 3-0- (CH ₂ ) 3- or (CH ₂ ) 3 ~ (CH ₂ ) 3- when R and R 'are all two of

phenyl groups. 2. Diphosphine dioxide, characterized in that it is chosen from 4-oxa-l, 7-heptamethylene bis dodecylphenyl phosphine dioxide, - 1, 8-octamethylene bis dodecylphenyl phosphine dioxide, 1, -bis ( 3-dodecylphenylphosphinopropoxy dioxide) benzene, - 5.13 - 5.13 dioxide - didodecyl-1, 9-dioxa-5, 13-diphosphacyclohexadecane. 4-oxa-1,7-heptamethylene bis (2'-ethoxyethyl) phenylphosphine dioxide, 4-oxa-l, 7-heptamethylene (2'-ethoxyethyl) phenylphosphine diphenyl phosphine dioxide, and 1,4-bis [3- (3'-ethoxypropyl) phenylphosphinopropoxy dioxide] benzene. 3. Process for the preparation of diphosphine dioxide of formula:

in which R ¹ , R ² , R ³ , R ⁴ and Q have the meanings given in claim 1, characterized in that it consists in subjecting a basic phosphonium disel of formula:

in which R ¹ , R ² , R ³ , R ⁴ and Q have the meanings given above, R ^ and R ⁸ are benzyl or phenyl groups and X is a halogen atom, to transform it into diphosphine dioxide of formula (I). 4. Process for the preparation of diphosphine dioxide of formula:

in which R, R ', Q and Q' have the meanings given in claim 1, characterized in that it consists in subjecting to basic hydrolysis a phosphonium disel of formula:

wherein R, R, Q and Q have the meanings given above, R ⁷ and R ⁸ are benzyl or phenyl groups, and X is a halogen atom. 5. Phosphonium disel of formula: ^R i R ³ R2_ pΦ-QP®. R, 2X "(III) R ⁷ - R ⁸ in which - R ¹ , R ² , R ³ , R ⁴ and Q have the meanings given in claim 1, R ⁷ and R ⁸ which may be the same or different, are benzyl or phenyl groups and X is a halogen atom. 6. Phosphonium disel of formula

wherein R, R ', Q and Q' have the meanings given in claim 1, R ⁷ and R ⁸ represent a benzyl or phenyl group, and X is a halogen atom. 7. Disel according to any one of claims 5 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, -bis (3-dodecyldiphenyl phosphoniopropoxy) benzene dibromide, - 4-oxa-l, 7-heptamethylene bis (2'-methoxyethyl) diphenyl phosphonium diiodide , and - the diiodide of 1, -bis [3- (3'-methoxypropyl) diphenyl phosphoniopropoxy] -benzene. 9. Phosphonium disel according to claim 6, characterized in that it is the diiodide of 5, 13-didodecyl-5, 13-diphenyl-l, 9-dioxa- 5, 13-diphosphonia cyclohexadecane. 10. Process for the separation of the actinide (s) present in an aqueous solution, characterized in that it consists in bringing the aqueous solution with an immiscible phase comprising at least one diphosphine dioxide corresponding to one of the following formulas:

in which: - R ¹ , R ² , R ³ and R ⁴ 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 groups, 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 identical or different represent a group chosen from alkyl groups, linear or branched, unsubstituted or substituted by at least one group chosen from alkoxy, carboxy, hydroxy and amino groups; aryl groups unsubstituted or substituted by at least one group chosen from alkyl, alkoxy, carboxy, hydroxy and amino groups; - Q and Q 'which may be identical or different, represent a group of formula:

- (CH ₂ ) _m -CH = CH- (CH ₂ ) _n -, - (CH ₂ ) _m -C≡C- (CH ₂ ) _n -, - (CH ₂ ) _p - [0- (CH ₂ ) _q ] _r -, - (CH ₂ ) _p - [S- (CH ₂ ) _q ] _r _, - (CH ₂ ) _p - [0-R ⁵ -0- (CH ₂ ) _q ] _r -, or - (CH ₂ ) _p - [N (R ⁶ ) - (CH ₂ ) _q ] _r - in which R ⁵ represents a phenylene group or a bivalent group derived from a heterocyclic ring, R ⁶ represents H or an alkyl group, and 1, m, n, p, q and r are whole numbers such that 3 <1 <16 3 <q <16 1 <m <16 1 <n <16 1 <r <16 3 <P <16 provided that, in formula (I), R- is different from R ² or R ³ is different from R ⁴ when Q represents (CH ₂ ) !, to extract the actinide (s) ) in said immiscible phase. 11. Method according to claim 10, characterized in that the immiscible phase is an organic liquid phase constituted by an organic solvent containing in solution the (the) oxide (s) of phosphine. 12. Method according to claim 11, characterized in that the organic solvent is a nitrophenylalkylether. 13. Method according to any one of claims 10 to 12, characterized in that the actinides (s) extracted (s) are recovered in the immiscible phase by bringing it into contact with a solution aqueous re-extraction having a pH of 1 to 7. 14. Method according to claim 10, characterized in that the immiscible phase is constituted by a liquid membrane comprising the phosphine oxide (s), one of the faces of the membrane being in contact with the aqueous solution containing actinides and the other side of the membrane being in contact with an aqueous re-extraction solution. 15. Method according to any one of claims 13 and 14, characterized in that the aqueous re-extraction solution is an aqueous solution of oxalic acid, citric acid or a salt of these acids. 16. Method according to claim 14, characterized in that the liquid membrane is a supported liquid membrane constituted by a microporous membrane whose pores are filled with diphosphine dioxide (s) in solution in an organic solvent immiscible with water. 17. The method of claim 16, characterized in that the organic solvent is a nitrophenylalkylether. 18. Method according to any one of claims 10 to 17, characterized in that the diphosphine dioxide is chosen from - 1,4-bis (dioxide 3-diphenylphosphinopropoxy) benzene, 4-oxa-l, 7-heptamethylene dioxide bis dodecylphenyl phosphine, - 1,8-octamethylene dioxide bis dodecylphenyl phosphine, 1,4-bis (3-dodecylphenylphosphinopropoxy dioxide) benzene, - 5.13 - 5.13 dioxide - didodecyl-1, 9-dioxa-5, 13- diphosphacyclohexadecane, - 4-oxa-l, 7-heptamethylene bis (2'-ethoxyethyl) phenylphosphine dioxide, dioxide 4-oxa-1,7-heptamethylene (2'-ethoxyethyl) phenylphosphine diphenyl phosphine, and 1,4-bis [3- (3'-methoxypropyl) phenylphosphinopropoxy dioxide] benzene. 19. Method according to any one of claims 10 to 18, characterized in that the actinides are chosen from plutonium and neptunium.