ALKENYL (PERFLUOROALKYL) PHOSPHINIC ACIDS
20170240574 · 2017-08-24
Assignee
Inventors
- Nikolai (Mykola) IGNATYEV (Duisburg, DE)
- Michael Schulte (Bischofsheim, DE)
- Karsten Koppe (Marl-Polsum, DE)
- Vural Bilir (Duesseldorf, DE)
- Walter Frank (Wuppertal, DE)
Cpc classification
B01J41/13
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3204
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3265
PERFORMING OPERATIONS; TRANSPORTING
Y02P10/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C08F112/14
CHEMISTRY; METALLURGY
C08F12/14
CHEMISTRY; METALLURGY
B01J20/3085
PERFORMING OPERATIONS; TRANSPORTING
C22B3/384
CHEMISTRY; METALLURGY
B01J41/04
PERFORMING OPERATIONS; TRANSPORTING
C07F9/5316
CHEMISTRY; METALLURGY
International classification
C07F9/30
CHEMISTRY; METALLURGY
B01J41/04
PERFORMING OPERATIONS; TRANSPORTING
B01J41/13
PERFORMING OPERATIONS; TRANSPORTING
C22B3/24
CHEMISTRY; METALLURGY
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
C07F9/53
CHEMISTRY; METALLURGY
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
C08F112/14
CHEMISTRY; METALLURGY
B01J20/32
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to alkenyl(perfluoroalkyl)phosphinic acids, to the preparation and intermediates thereof, to the use thereof as monomers for the preparation of oligomers and/or polymers, to the corresponding oligomers/polymers, to the corresponding support materials comprising the oligomers/polymers, and to the use thereof as ion exchangers, as catalysts or extraction medium and corresponding salts thereof.
Claims
1. Compounds of the formula I ##STR00065## where R.sub.f denotes a straight-chain or branched perfluoroalkyl group having 1 to 12 C atoms, A denotes H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms, B denotes —(CR.sub.1R.sub.2).sub.n—, [—(CR.sub.1R.sub.2).sub.m—O—(CR.sub.1R.sub.2).sub.m1—].sub.m2, arylene or substituted arylene, X denotes H, F and/or Cl, n denotes an integer from 0 to 20, m denotes an integer from 1 to 20, m.sub.1 denotes an integer from 0 to 8, m.sub.2 denotes an integer from 1 to 20 and R.sub.1 or R.sub.2 each, independently of one another, denote H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms.
2. Compounds according to claim 1, characterised in that R.sub.f denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms.
3. Compounds according to claim 1, characterised in that A and X are identical.
4. Compounds according to claim 1, characterised in that B denotes —(CR.sub.1R.sub.2).sub.n—, arylene or substituted arylene.
5. Process for the preparation of compounds of the formula I according to claim 1, characterised in that a) a compound of the formula II
(F).sub.x(R.sub.f).sub.4-xP—B—CX═CX-A II, where R.sub.f, A, B and X have a meaning indicated in claim 1 and x denotes 1 or 2, is hydrolysed, giving an intermediate compound of the formula IIIa as intermediate, ##STR00066## where R.sub.f, A, B and X have a meaning indicated in formula II, or b) a compound of the formula II
(F).sub.x(R.sub.f).sub.4-xP—B—CX═CX-A II, where R.sub.f, A, B and X have a meaning indicated in claim 1 and x denotes 1, 2 or 3, is reacted with a hexaalkyldisiloxane without or in the presence of a catalytic amount of water, where the alkyl groups of the hexaalkyldisiloxane each, independently of one another, denote a straight-chain or branched alkyl group having 1 to 4 C atoms, giving an intermediate compound of the formula III, ##STR00067## where R.sub.f, A, B and X a have a meaning indicated in formula II, which is subsequently hydrolysed.
6. Compounds of the formula IIIa, ##STR00068## where R.sub.f, A, B and X have a meaning indicated in claim 1.
7. A method for the preparation of oligomers or polymers which comprises oligomerizina or polymerizing a compound of claim 1.
8. Oligomer or polymer containing polymerised compounds of the formula I, according to claim 1, as monomer units.
9. Process for the preparation of oligomers or polymers according to claim 8, characterised in that compounds of the formula I, are polymerised, optionally together with further monomers and optionally in the presence of a crosslinking agent.
10. Process according to claim 9, characterised in that the polymerisation is carried out by means of free radicals
11. Process according to claim 9, characterised in that a homo-polymer is prepared.
12. Process according to claim 9, characterised in that the polymerisation is carried out without crosslinking agents.
13. Process according to claim 9, characterised in that the polymerisation is carried out in, on or at a support material.
14. Composite material comprising a support material and at least one compound according to claim 1.
15. An ion exchanger or as Brønsted acid catalyst material comprising a compound of claim 1 or a polymer or oligomer of a compound of claim 1.
16. A method for the extraction of cations of the rare earths from a solution which comprises contacting the solution with a material comprising a compound of claim 1 or a polymer or oligomer thereof.
17. A salt corresponding to the formula IV, ##STR00069## where the cations Kt.sup.+ in formula IV denotes an inorganic or organic cation and where R.sub.f denotes a straight-chain or branched perfluoroalkyl group having 1 to 12 C atoms, A denotes H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms, B denotes —(CR.sub.1R.sub.2).sub.n—, [—(CR.sub.1R.sub.2).sub.m—O—(CR.sub.1R.sub.2).sub.m1—].sub.m2, arylene or substituted arylene, X denotes H, F and/or Cl, n denotes an integer from 0 to 20, m denotes an integer from 1 to 20, m.sub.1 denotes an integer from 0 to 8, m.sub.2 denotes an integer from 1 to 20 and R.sub.1 or R.sub.2 each, independently of one another, denote H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms.
18. A polymer or oligomer comprising polymerized units of a salt of claim 17 as monomer units.
19. Composite material comprising a support material and at least one oligomer or polymer of claim 8.
20. Composite material comprising a support material and at least one polymer or oligomer of claim 19.
Description
EXAMPLE 1
Synthesis of allylfluorotris(pentafluoroethyl)phosphorane by Reaction of difluorotris(pentafluoroethyl)phosphorane and allylmagnesium bromide
[0289] ##STR00012##
[0290] Difluorotris(pentafluoroethyl)phosphorane, (C.sub.2F.sub.5).sub.3PF.sub.2 (82.8 g, 194 mmol), is initially introduced in a 500 ml round-bottomed flask, cooled (0° C.) and emulsified in diethyl ether (100 ml). Allylmagnesium bromide, CH.sub.2═CHCH.sub.2—MgBr (100 ml of a 1 mol/l solution in diethyl ether; 100 mmol), is added to this emulsion over the course of one hour. A white solid precipitates out, and the reaction mother liquor becomes a yellow colour. The suspension is stirred at 0° C. for 1 hour and at room temperature for 1 hour. The reaction suspension is subsequently filtered, and the solid is washed twice with diethyl ether (25 ml each time). The ether phases are combined and ether and excess (C.sub.2F.sub.5).sub.3PF.sub.2 are condensed off at 0° C. in vacuo (10.sup.−1 mbar). The yellow liquid remaining consists principally of product, (C.sub.2F.sub.5).sub.3PF—(CH.sub.2CH═CH.sub.2), and small amounts of (C.sub.2F.sub.5).sub.3PF.sub.2 and (C.sub.2F.sub.5).sub.3P═O. Pure allylfluorotris(pentafluoroethyl)phosphorane, (C.sub.2F.sub.5).sub.3PF(CH.sub.2CH═CH.sub.2) (37.1 g, 83 mmol), can be isolated as a clear and colourless liquid with a yield of 83% by condensation at 30° C. in vacuo (10.sup.−3 mbar). The isolated product is characterised by means of .sup.1H, .sup.19F and .sup.31P NMR spectra.
[0291] NMR (lock substance: CD.sub.3CN film; δ in ppm): .sup.1H NMR: 3.56 m (2H), 5.32 m (2H), 5.71 m (1H)
[0292] .sup.19F NMR: −7.3* d, .sup.1J.sub.F,P=827 Hz (1F), −81.9* m (9F), −122.0* d, .sup.2J.sub.F,P=80 Hz (6F)
[0293] .sup.31P NMR: −42.0 d, sep, t, d, .sup.1J.sub.P,F=822 Hz, .sup.2J.sub.P,F=78 Hz, .sup.2J.sub.P,H=14 Hz, .sup.3J.sub.P,H=5 Hz (1P)
[0294] * signals broadened
EXAMPLE 2
Synthesis of allylpentafluoroethylphosphinic acid by Hydrolysis of allylfluorotris(pentafluoroethyl)phosphorane in Water
[0295] ##STR00013##
[0296] Clear and colourless allylfluorotris(pentafluoroethyl)phosphorane, (C.sub.2F.sub.5).sub.3PF(CH.sub.2CH═CH.sub.2) (33.7 g, 75.2 mmol), is initially introduced in a 100 ml PFA round-bottomed flask, cooled (0° C.), and water (10 ml, .Math.555 mmol) is slowly added. The reaction is very exothermic and is cooled if necessary using ice (0° C.). The emulsion is stirred at 0° C. to 18° C. for 1 hour, at 35° C. for 1.5 hours, at 50° C. for 1.5 hours and finally at 80° C. for 3 hours. Evolution of gas can be observed constantly. Excess water is subsequently condensed off at 50° C. to 65° C. in vacuo (10.sup.−3 mbar). The crude product remaining is transferred quantitatively into a 100 ml glass flask and condensed at 100° C. in vacuo (10.sup.−3 mbar). Allylpentafluoroethylphosphinic acid, (C.sub.2F.sub.5)(CH.sub.2CH═CH.sub.2)P(O)OH (14.2 g, 63.5 mmol), can be isolated as a clear and colourless liquid with a yield of 84%. The isolated product is characterised by means of .sup.1H, .sup.19F and .sup.31P NMR spectra.
##STR00014##
[0297] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 2.24 m (2H), 4.74 m (2H), 5.14 m (1H). .sup.19F NMR: −81.9 m (3F), −128.4 d, .sup.2J.sub.F,P=73 Hz (2F). .sup.31P NMR: 25.4 t, t, d .sup.2J.sub.P,F=83 Hz, .sup.2J.sub.P,H=18 Hz, .sup.3J.sub.P,H=5 Hz (1P).
EXAMPLE 3
Synthesis of allylbis(pentafluoroethyl)phosphine oxide by Hydrolysis of allylfluorotris(pentafluoroethyl)phosphorane in Water
[0298] ##STR00015##
[0299] Clear and colourless allylfluorotris(pentafluoroethyl)phosphorane, (C.sub.2F.sub.5).sub.3PF(CH.sub.2CH═CH.sub.2) (11.45 g, 25.5 mmol), is initially introduced in a 23 mm (internal diameter) FEP reactor, cooled (0° C.), and water (1.7 ml, 94 mmol) is added. Two phases form and evolution of gas can be observed. The reaction emulsion is stirred at 0° C. for 1.5 hours and at room temperature for 30 minutes. A conversion of 79% to allylbis(pentafluoroethyl)phoshine oxide, (C.sub.2F.sub.5).sub.2P(O)(CH.sub.2CH═CH.sub.2), can be detected. Secondary compounds are [H(H.sub.2O).sub.n][(C.sub.2F.sub.5).sub.3PF.sub.3] (21%) and traces of bis(pentafluoroethyl)phosphinic acid, (C.sub.2F.sub.5).sub.2P(O)OH. The compounds can easily be separated from one another using methods which are known to the person skilled in the art. The mixture can be used without further purification for the further hydrolysis (Example 2). The product is characterised by means of .sup.1H, .sup.19F and .sup.31P NMR spectra.
##STR00016##
[0300] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 3.40 m (2H), 5.56 m (2H), 5.80 m (1H). .sup.19F NMR: −81.9 m (6F), −122.1 d, m .sup.2J.sub.FA,P=79 Hz, .sup.2J.sub.FB,P=71 Hz, J.sub.FA,FB=341 Hz (2F.sub.A), −124.1 d, m, .sup.2J.sub.FA′,P=79 Hz, .sup.2J.sub.FB′,P=71 Hz, J.sub.FA′,FB′=310 Hz (2F.sub.B). .sup.31P NMR: 36.4 t, t .sup.2J.sub.P,FA=.sup.2J.sub.P,FA′=79 Hz, .sup.2J.sub.P,FB=.sup.2J.sub.P,FB′=71 Hz (1P).
EXAMPLE 4
Synthesis of but-3-en-1-ylmagnesium bromide
[0301] ##STR00017##
[0302] Magnesium turnings (15.81 g, 650 mmol) in diethyl ether (300 ml) are initially introduced in a 500 ml glass round-bottomed flask, and 4-bromo-1-butene (96.20 g, 713 mmol) is added over the course of 2 hours at room temperature. The brown suspension is stirred at room temperature for a further 30 minutes and subsequently filtered. But-3-en-1-ylmagnesium bromide (91%, -592 mmol) in diethyl ether can be obtained as a brown solution. The only by-product is 1,7-octadiene (9%). This solution is used without further purification. The product is characterised by means of .sup.1H and .sup.13C NMR spectra.
##STR00018##
[0303] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: −0.57 t .sup.3J.sub.H,H=8 Hz (2H.sup.a), 2.15 t, d, d, d .sup.3J.sub.H,H=8 Hz, .sup.3J.sub.H,H=7 Hz, .sup.4J.sub.H,H=1.5 Hz, .sup.4J.sub.H,H=1.1 Hz (2H.sup.b), 4.52 d, d, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=3 Hz, .sup.4J.sub.H,H=1.1 Hz (1 H.sup.e), 4.72 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=3 Hz, .sup.4J.sub.H,H=1.5 Hz (1 H.sup.d), 5.85 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=7 Hz (1 H.sup.c)
[0304] .sup.13C NMR: 7.5 t, m .sup.1J.sub.C,H=108 Hz, (1C.sup.a), 34.1 t, d, d, d .sup.1J.sub.C,H=123 Hz, .sup.2J.sub.C,H=5 Hz, .sup.3J.sub.C,H=5 Hz , .sup.3J.sub.C,H=5 Hz (1C.sup.b), 108.7 d, d, t .sup.1J.sub.C,H=155 Hz, .sup.1J.sub.C,H=152 Hz, .sup.3J.sub.C,H=6 Hz (1C.sup.d), 148.3 d, t, m .sup.1J.sub.C,H=148 Hz, .sup.2J.sub.C,H=6 Hz (1C.sup.c).
EXAMPLE 5
Synthesis of di(but-3-en-1-yl)zinc by Reaction of but-3-en-1-ylmagnesium bromide and Zinc Chloride
[0305] ##STR00019##
[0306] Zinc chloride (37.14 g, 272 mmol) is suspended in diethyl ether (500 ml) in a 100 ml glass round-bottomed flask, and the but-3-en-1-ylmagnesium bromide solution (592 mmol in diethyl ether (300 ml)) described in Example 4 is added over the course of 4 hours. A bulky pale-grey precipitate precipitates out. The suspension is stirred at room temperature for 12 h and then filtered. The grey residue is washed with diethyl ether (60 ml). The yellow filtrate and the wash solution are combined, and the majority of the ether is condensed off at 0° C. in vacuo (10.sup.−3 mbar). The product is condensed out of the suspension at 30° C. to 40° C. in vacuo (10.sup.−3 mbar) into a cooled (−196° C.) trap. Residues of diethyl ether and 1,7-octadiene can be removed in a further condensation at −20° C. to −15° C. in vacuo (10.sup.−3 mbar). Further purification can be achieved by re-condensation of the product at 40° C. in vacuo (10.sup.−3 mbar). Di(but-3-en-1-yl)zinc (40.59 g, 231 mmol) can be isolated as a clear and colourless liquid with a yield of 85% and a purity of 99%. The isolated product is characterised by means of .sup.1H and .sup.13C NMR spectra.
##STR00020##
[0307] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 0.40 t .sup.3J.sub.H,H=8 Hz (4H.sup.a), 2.24 t, d, d, d .sup.3J.sub.H,H=8 Hz, .sup.3J.sub.H,H=6 Hz, .sup.4J.sub.H,H=1.7 Hz, .sup.4J.sub.H,H=1.2 Hz (4H.sup.b), 4.84 d, d, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=1.8 Hz, .sup.4J.sub.H,H=1.2 Hz (2H.sup.e), 4.94 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=1.8 Hz, .sup.4J.sub.H,H=1.7 Hz (2H.sup.d), 5.92 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=6 Hz (2H.sup.c). .sup.13C NMR: 15.9 t, t, d, t .sup.1J.sub.C,H=121.3 Hz, .sup.2J.sub.C,H=4.1 Hz, .sup.2J.sub.C,H=4.0 Hz, .sup.3J.sub.C,H=1.0 Hz (2C.sup.a), 31.3 t, m .sup.1J.sub.C,H=121.3 Hz (2C.sup.b), 113.1 d, d, t, m .sup.1J.sub.C,H=157.5 Hz, .sup.1J.sub.C,H=152.3 Hz, .sup.3J.sub.C,H=6.1 Hz (2C.sup.d), 145.0 d, t, d, d, m .sup.1J.sub.C,H=121.3 Hz, .sup.2J.sub.C,H=6.2 Hz, .sup.2J.sub.C,H=6.2 Hz, .sup.2J.sub.C,H=5.8 Hz (2C.sup.c).
EXAMPLE 6
Synthesis of bis(pentafluoroethyl)trifluorophosphorane
[0308] ##STR00021##
[0309] Pale-yellow hexylmethylimidazolium bis(pentafluoroethyl)tetrafluorophosphate, [C.sub.6MIM][(C.sub.2F.sub.5).sub.2PF.sub.4] (203.0 g, 396 mmol), is initially introduced in a 500 ml glass round-bottomed flask, warmed (100° C.), and freshly distilled yellow SbCl.sub.5 (137.7 g; 460 mmol) is added dropwise over the course of 2.5 h. Bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3, (bp 46° C.), formed is condensed directly into a cooled (−78° C.) 300 ml Young U-trap. After a further 30 min at 100° C. and 15 min at 150° C., bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3 (122.1 g; 375 mmol), can be isolated in the trap as a pale-yellow liquid in a yield of 95% (purity 98%). The phosphorane can be used without further purification for subsequent experiments. The isolated product is characterised by means of .sup.19F and .sup.31P NMR spectra.
##STR00022##
[0310] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.19F NMR: −55.2 d, qui, sep .sup.1J.sub.F,P=1145 Hz, .sup.3J.sub.F,F=11 Hz, .sup.4J.sub.F,F=7 Hz (3F), −84.1 q, d .sup.4J.sub.F,F=7 Hz, .sup.3J.sub.F,P=2 Hz (6F), −119.8 d, q .sup.2J.sub.F,P=127 Hz, .sup.3J.sub.F,F=11 Hz (4F)
[0311] .sup.31P NMR: −40.1 q, qui, sep .sup.1J.sub.P,F=1145 Hz, .sup.2J.sub.P,F=127 Hz, .sup.3J.sub.P,F=2.0 Hz (1P).
EXAMPLE 7
Synthesis of bis(pentafluoroethyl)(but-3-en-1-yl)difluorophosphorane by Reaction of bis(pentafluoroethyl)trifluorophosphorane and di(but-3-en-1-yl)zinc
[0312] ##STR00023##
[0313] Di(but-3-en-1-yl)zinc (24.27 g, 138 mmol) is dissolved in n-pentane (350 ml) in a 1000 ml glass round-bottomed flask, and bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3 (76.4 g, 234 mmol), is added over the course of 7.5 hours at room temperature. A white solid precipitates out. The suspension is stirred at room temperature for 1.5 hours, and n-pentane is subsequently condensed off at −40° C. to −25° C. in vacuo (10.sup.−3 mbar). The product which remains is condensed at room temperature in vacuo (10.sup.−3 mbar). Bis(pentafluoroethyl)(but-3-en-1-yl)difluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2—(CH.sub.2CH.sub.2CH═CH.sub.2) (82.08 g, 227 mmol), can be isolated as a clear and colourless liquid with a yield of 97% and a purity of 91%. Bis(pentafluoroethyl)difluorocyclopropylmethylphosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(CH.sub.2-c-C.sub.3H.sub.5) (6%) and di(but-3-en-1-yl)zinc (3%) are detected as by-products. This mixture is used without further purification. The impurities can be separated using methods which are known to the person skilled in the art. The product is characterised by means of .sup.1H, .sup.19F, .sup.13C and .sup.31P NMR spectra.
##STR00024##
[0314] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 2.35 m (2H.sup.a), 2.47 m (2H.sup.b), 5.02 d, m
[0315] .sup.3J.sub.H,H=10 Hz (1H.sup.e), 5.05 d, m .sup.3J.sub.H,H=17 Hz (1H.sup.d), 5.71 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=6 Hz (1H.sup.c)
[0316] .sup.13C NMR: 25.8 t, d, t, m .sup.1J.sub.C,H=133 Hz, .sup.3J.sub.C,F=8 Hz, .sup.2J.sub.C,P=4 Hz (1C.sup.b), 29.0 t, d, t, m .sup.1J.sub.C,H=123 Hz, .sup.1J.sub.C,P=108 Hz, .sup.2J.sub.C,F=17 Hz (1C.sup.a), 113.3 L t, d, q, m .sup.1J.sub.C,F=284 Hz, .sup.1J.sub.C,P=86 Hz, .sup.2J.sub.C,F=42 Hz (2CF.sub.2), 116.0 d, d, t, d, m .sup.1J.sub.C,H=159 Hz, .sup.1J.sub.C,H=154 Hz, .sup.3J.sub.C,H=6 Hz, .sup.4J.sub.C,P=1.5 Hz (1C.sup.d), 118.4 q, t, d, m .sup.1J.sub.C,F=286 Hz, .sup.2J.sub.C,F=32 Hz, .sup.2J.sub.C,P=27 Hz (2CF.sub.3), 134.6 d, d, m .sup.1 J.sub.C,H=156 Hz, .sup.3J.sub.C,P=21 Hz (1C.sup.c)
[0317] .sup.19F NMR: −49.7 d, t, q, m .sup.1J.sub.F,P=876 Hz, .sup.3J.sub.F,F=14 Hz, .sup.4J.sub.F,F=11 Hz (2F), −83.6 t .sup.4J.sub.F,F=11 Hz (6F), −118.0 d, t .sup.2J.sub.F,P=112 Hz, .sup.3J.sub.F,F=14 Hz (4F) .sup.31P NMR: −31.5 t, qui, t, t .sup.1J.sub.P,F=876 Hz, .sup.2J.sub.P,F=112 Hz, .sup.2J.sub.P,H=18 Hz, .sup.3J.sub.P,H=13 Hz (1P).
EXAMPLE 8
Synthesis of bis(pentafluoroethyl)(but-3-en-1-yl)phosphine oxide by Reaction of bis(pentafluoroethyl)(but-3-en-1-yl)difluorophosphorane and hexamethyldisiloxane using Catalytic Amounts of H.SUB.2.O
[0318] ##STR00025##
[0319] Hexamethyldisiloxane (76.2 g, 469 mmol) and H.sub.2O (619 mg; 34.4 mmol) are added to bis(pentafluoroethyl)(but-3-en-1-yl)difluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(CH.sub.2CH.sub.2CH═CH.sub.2), from Example 7 (151.4 g, 418 mmol), containing bis(pentafluoroethyl)difluorocyclopropylmethylphosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(CH.sub.2-c-C.sub.3H.sub.5) (5%) and di(but-3-en-1-yl)zinc (3%)] in a 250 ml glass round-bottomed flask, and the mixture is stirred at 100° C. for 3.5 hours with evolution of gas. The product is subsequently condensed at room temperature to 30° C. in vacuo (10.sup.−3 mbar). Bis(pentafluoroethyl)(but-3-en-1-yl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(CH.sub.2CH.sub.2CH═CH.sub.2) (131.2 g; 386 mmol), can be isolated as a clear and colourless liquid with a yield of 92%. By-products are bis(pentafluoroethyl)cyclopropylmethylphosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(CH.sub.2-c-C.sub.3H.sub.5) (5%, 6.8 g; 20 mmol), trimethylfluorosilane and hexamethyldisiloxane (13.7 g). This mixture is used without further purification. The compounds can be separated using methods which are known to the person skilled in the art.
[0320] The product, bis(pentafluoroethyl)(but-3-en-1-yl)-phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(CH.sub.2CH.sub.2CH═CH.sub.2), is characterised by means of .sup.1H, .sup.13C, .sup.19F and .sup.31P NMR spectra.
##STR00026##
[0321] NMR (lock substance: CDCl.sub.3; δ in ppm) .sup.1H NMR: 2.44 m (2H.sup.a), 2.56 m (2H.sup.b), 5.13 d, d, t .sup.3J.sub.H,H=10 Hz, 2J.sub.H,H=1.2 Hz, .sup.4J.sub.H,H=1.0 Hz (1H.sup.e), 5.16 d, t, d .sup.3J.sub.H,H=17 Hz, .sup.4J.sub.H,H=1.5 Hz, .sup.2J.sub.H,H=1.2 Hz (1H.sup.d), 5.86 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=6 Hz (1H.sup.c) .sup.13C NMR: 23.8 t, d, t, m .sup.1J.sub.C,H=133 Hz, .sup.1J.sub.C,P=64 Hz, .sup.2J.sub.C,H=6 Hz (1C.sup.a), 24.1 t, t, d, m .sup.1J.sub.C,H=132 Hz, .sup.2J.sub.C,H=6 Hz, .sup.2J.sub.C,H=5 Hz (1C.sup.b), 112.9 d, d, d, q, m .sup.1J.sub.C,FA=.sup.1J.sub.C,FA′=286 Hz, .sup.1J.sub.C,FB=.sup.1J.sub.C,FB′=.sup.1J.sub.C,P=88 Hz, .sup.2J.sub.C,F=41 Hz (2CF.sub.2), 117.3 d, d, t, d, m .sup.1J.sub.C,H=160 Hz, .sup.1J.sub.C,H=154 Hz, .sup.3J.sub.C,H=6 Hz, .sup.4J.sub.C,P=0.9 Hz (1C.sup.d), 118.4 q, d, d, d, m .sup.1J.sub.C,F=287 Hz, .sup.2J.sub.C,FA=.sup.2C,FA′=31 Hz, .sup.2J.sub.C,FB=.sup.2J.sub.C,FB′=30 Hz .sup.2J.sub.C,P=17 Hz (2CF.sub.3), 134.9 d, d, t, d, d .sup.1J.sub.C,H=156 Hz, .sup.3J.sub.C,P=16 Hz, .sup.2J.sub.C,H=6 Hz, .sup.2J.sub.C,H=3 Hz, .sup.2J.sub.C,H=3 Hz (1C.sup.c) .sup.19F NMR: −80.3 d, m .sup.3J.sub.F,P=1.2 Hz (6F), −121.7 d, m .sup.2J.sub.FA,P=77 Hz, .sup.2J.sub.FB,P=69 Hz, .sup.2J.sub.FA,FB=340 Hz (2F.sub.A), −123.6 d, m .sup.2J.sub.FA′,P=77 Hz, .sup.2J.sub.FB′,P=69 Hz, .sup.2J.sub.FA′,FB′=310 Hz (2F.sub.B)
[0322] .sup.31P NMR: 37.8 t, t, t, t, sep .sup.2J.sub.P,FA=.sup.2J.sub.P,FA′=77 Hz, .sup.2J.sub.P,FB=.sup.2J.sub.P,FB′=69 Hz, .sup.2J.sub.P,H=10 Hz , .sup.3J.sub.P,H=10 Hz, .sup.3J.sub.P,F=1.2 Hz (1P).
EXAMPLE 9
Synthesis of (but-3-en-1-yl)(pentafluoroethyl)phosphinic acid by Hydrolysis of bis(pentafluoroethyl)(but-3-en-1-yl)phosphine oxide
[0323] ##STR00027##
[0324] Bis(pentafluoroethyl)(but-3-en-1-yl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)—(CH.sub.2CH.sub.2CH═CH.sub.2) (130.3 g, 383 mmol), from Example 8 is emulsified with water (100 ml) in a 250 ml glass round-bottomed flask and warmed (50° C.). The emulsion is stirred at 50° C. for 17 hours with constant evolution of gas. All volatile constituents are subsequently condensed off at room temperature in vacuo (10.sup.−3 mbar). The product which remains is distilled at 130° C. in vacuo (10.sup.−3 mbar). (Pentafluoroethyl)(but-3-en-1-yl)phosphinic acid, (C.sub.2F.sub.5)—(CH.sub.2CH.sub.2CH═CH.sub.2)P(O)OH (89.7 g; 375 mmol), can be isolated as a clear and colourless liquid (94.0 g) with a yield of 93%. The only by-product is pentafluoroethyl(cyclopropylmethyl)phosphinic acid, (C.sub.2F.sub.5)(CH.sub.2-c-C.sub.3H.sub.5)—P(O)OH (4.3 g; 18 mmol), which results from bis(pentafluoroethyl)cyclopropylmethylphosphine oxide in the starting material. The two compounds can be separated using methods which are known to the person skilled in the art. The isolated product is characterised by means of .sup.1H, .sup.13C, .sup.19F and .sup.31P NMR spectra.
##STR00028##
[0325] NMR (lock substance: CDCl.sub.3; δ in ppm) .sup.1H NMR: 2.02 m (2H.sup.a), 2.41 m (2H.sup.b), 5.06 d, t, d .sup.3J.sub.H,H=10 Hz, .sup.4J.sub.H,H=1.4 Hz, .sup.2J.sub.H,H=1.1 Hz (1H.sup.e), 5.10 d, t, d .sup.3J.sub.H,H=17 Hz, .sup.4J.sub.H,H=1.4 Hz, .sup.2J.sub.H,H=1.2 Hz (1H.sup.d), 5.83 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=6 Hz (1H.sup.c), 10.86 s Δv.sub.1/2=7 Hz (1OH)
[0326] .sup.13C NMR: 24.5 t, d, m .sup.1J.sub.C,H=129 Hz, .sup.2J.sub.C,P=5 Hz (1C.sup.b), 25.1 t, d, m .sup.1J.sub.C,H=129 Hz, .sup.1J.sub.C,P=102 Hz (1C.sup.a), 111.6 t, d, q .sup.1J.sub.C,F=276 Hz, .sup.1J.sub.C,P=127 Hz, .sup.2J.sub.C,F=40 Hz, (1CF.sub.2), 116.5 d, d, t .sup.1J.sub.C,H=159 Hz, .sup.1J.sub.C,H=154 Hz, .sup.3J.sub.C,H=6 Hz (1C.sup.d), 119.0 q, t, d .sup.1J.sub.C,F=286 Hz, .sup.2J.sub.C,F=31 Hz, .sup.2J.sub.C,P=16 Hz (1CF.sub.3), 136.3 d, d, t, d, d .sup.1J.sub.C,H=155 Hz, .sup.3J.sub.C,P=17 Hz, .sup.2J.sub.C,H=6 Hz, .sup.2J.sub.C,H=3 Hz, .sup.2J.sub.C,H=3 Hz (1C.sup.c)
[0327] .sup.19F NMR: −80.8 s Δv.sub.1/2=5 Hz (3F), −121.5 d .sup.2J.sub.F,P=81 Hz (2F)
[0328] .sup.31P NMR: 34.5 t .sup.2J.sub.P,F=81 Hz (1P).
EXAMPLE 10
Synthesis of undec-10-en-1-ylmagnesium bromide by Reaction of 11-bromo-1-undecene and Magnesium
[0329] ##STR00029##
[0330] Magnesium turnings (0.53 mg, 21.6 mmol) in diethyl ether (20 ml) are initially introduced in a 100 ml glass round-bottomed flask, and 11-bromo-1-undecene (5.25 g, 22.5 mmol) in diethyl ether (20 ml) is added over the course of 1 hour. The yellow suspension is stirred at room temperature for 30 minutes and subsequently filtered. Undec-10-en-1-ylmagnesium bromide (83%, -18 mmol) in diethyl ether can be obtained as a yellow solution. By-product is 1,21-docosadiene (11 mol %). This solution is used without further purification. The isolated product is characterised by means of 1H and .sup.13C NMR spectra.
##STR00030##
[0331] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: −0.54 t .sup.3J.sub.H,H=8 Hz (2H.sup.a), 1.26-1.29° t.sup.3J.sub.H,H=7 Hz (10H.sup.c-g), 1.36° t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.h), 1.50 t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.b), 2.01 t, d, t .sup.3J.sub.H,H=7 Hz, 3J.sub.H,H=7 Hz, .sup.4J.sub.H,H=1 Hz (2H.sup.i), 4.86 d, d, t, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=1 Hz, .sup.5J.sub.H,H=1 Hz (1H.sup.m), 4.93 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=2 Hz (1H.sup.l), 5.75 d, d, t
[0332] .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=7 Hz (1H.sup.k) .sup.13C{.sup.1H} NMR: 8.5 (1C.sup.a), 29.7 (1C.sup.b,d-h), 29.9 (1C.sup.b,d-h), 30.3° (1C.sup.b,d-h), 30.4° (1C.sup.b,d-h), 30.4° (1C.sup.b,d-h), 30.6 (1C.sup.b,d-h), 34.5 (1C.sup.i), 39.0 (1C.sup.c), 114.2 (1C.sup.l), 139.4 (1C.sup.k).
[0333] ° signals superimposed
EXAMPLE 11
Synthesis of bis(undec-10-en-1-yl)zinc by Reaction of undec-10-en-1-ylmagnesium bromide and Zinc Chloride
[0334] ##STR00031##
[0335] Zinc chloride, ZnCl.sub.2 (2.99 g, 21.9 mmol), is suspended in diethyl ether (40 ml) in a 250 ml glass round-bottomed flask, and a solution of undec-10-en-1-ylmagnesium bromide (45.2 mmol, contains 17 mol % of 1,21-docosadiene) in diethyl ether (120 ml) is added over the course of 45 minutes. A bulky white solid rapidly precipitates out. The suspension is filtered under inert gas, and the residue is washed with diethyl ether (10 ml). The pale-yellow filtrate is evaporated together with the wash solution at room temperature in vacuo (10.sup.−3 mbar). The bulky suspension formed is extracted three times with n-pentane (20 ml each time) and filtered under inert conditions. The n-pentane phases are subsequently combined, and n-pentane is condensed off at 40° C. in vacuo (10.sup.−3 mbar). Di(undec-10-en-1-yl)zinc (6.17 g, 16.6 mmol) can be isolated as a clear and yellow liquid with a yield of 76%. The only by-product is 1,21-docosadiene (3.18 g, 10.4 mmol, 39 mol %). The two compounds can be separated using methods which are known to the person skilled in the art. This solution is used without further purification. The product, di(undec-10-en-1-yl)zinc, is characterised by means of .sup.1H and .sup.13C NMR spectra.
##STR00032##
[0336] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 0.39 t .sup.3J.sub.H,H=8 Hz (4H.sup.a), 1.26-1.28° t .sup.3J.sub.H,H=7 Hz (20H.sup.c-g), 1.36° t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (4H.sup.h), 1.55 t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (4H.sup.b), 2.00 t, d .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (4H.sup.i), 4.87 d, d, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=1 Hz (2H.sup.m), 4.93 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=2 Hz (2H.sup.l), 5.73 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.k)
[0337] .sup.13C NMR: 16.8 t, m .sup.1J.sub.C,H=120 Hz (2C.sup.a), 26.9 t, m .sup.1J.sub.C,H=124 Hz (2C.sup.b), 29.5° t, m .sup.1J.sub.C,H=126 Hz (2C.sup.d-h), 29.8° t, m .sup.1J.sub.C,H=126 Hz (2C.sup.d-h), 30.2° t, m .sup.1J.sub.C,H=126 Hz (2C.sup.d-h), 30.3° t, m .sup.1J.sub.C,H=126 Hz (2C.sup.d-h), 30.4° t, m .sup.1J.sub.C,H=126 Hz (2C.sup.d-h), 34.4 t, m .sup.1J.sub.C,H=126 Hz (2C.sup.i), 37.1 t, m .sup.1J.sub.C,H=124 Hz (2C.sup.c), 114.6 d, d, t .sup.1J.sub.C,H=157 Hz, .sup.1J.sub.C,H=153 Hz, .sup.3J.sub.C,H=6 Hz (2C.sup.l), 139.0 d, d, d, t .sup.1J.sub.C,H=150 Hz, .sup.2J.sub.C,H=6 Hz, .sup.2J.sub.C,H=6 Hz, .sup.2J.sub.C,H=6 Hz (2C.sup.K).
[0338] * signals broadened
[0339] ° signals superimposed
EXAMPLE 12
Synthesis of bis(pentafluoroethyl)difluoro(undec-10-en-1-yl)phosphorane by Reaction of di(undec-10-en-1-yl)zinc and bis(pentafluoroethyl)trifluorophosphorane
[0340] ##STR00033##
[0341] Di(undec-10-en-1-yl)zinc (2.39 g, 6.43 mmol; additionally contains 1.53 g of 1,21-docosadiene) is dissolved in n-pentane (40 ml) in a 100 ml glass round-bottomed flask. Bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3 (2.54 g, 7.79 mmol), is added to this solution over the course of 10 minutes. The solution is stirred at room temperature for 30 minutes. A suspension forms. The conversion (96%, 7.48 mmol) to bis(pentafluoroethyl)difluoro(undec-10-en-1-yl)phosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(C.sub.9H.sub.18CH═CH.sub.2), is virtually quantitative. The only by-product formed besides ZnF.sub.2 is bis(pentafluoroethyl)(cyclopropyloctyl)difluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(C.sub.8H.sub.16-cyclo-C.sub.3H.sub.5) (4%). In addition, 1,21-docosadiene from the starting material (see Example 10) are also in the suspension. The compounds can be separated using methods which are known to the person skilled in the art. The suspension is used here without further purification. The product is characterised by means of .sup.1H, .sup.13C{.sup.1H}, .sup.19F and .sup.31P NMR spectra.
##STR00034##
[0342] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 1.28-1.31° s (10H.sup.c-g), 1.37° t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.h), 1.66 d, t, t .sup.3J.sub.H,P=13 Hz, .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.b), 2.02 t, d, t, D .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz, .sup.4J.sub.H,H=1.6 Hz, .sup.4J.sub.H,H=1.2 Hz (2H.sup.i), 2.37 d, t, t .sup.2J.sub.H,P=18 Hz, .sup.3J.sub.H,F=17 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.a), 4.87 d, d, t, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=1.9 Hz, .sup.4J.sub.H,H=1.2 Hz, .sup.5J.sub.H,H=0.9 Hz (1H.sup.m), 4.94 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=1.9 Hz, .sup.4J.sub.H,H=1.6 Hz (1H.sup.l), 5.74 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=7 Hz (1H.sup.k)
[0343] .sup.13C{.sup.1H} NMR: 22.1 t, d .sup.3J.sub.C,F=7 Hz, .sup.2J.sub.C,P=6 Hz (1C.sup.b), 29.0 d .sup.3J.sub.C,P=1.7 Hz (1C.sup.c), 29.3 (1C.sup.d-h), 29.5° (1C.sup.d-h), 29.5° (1C.sup.d-h), 30.0° d, t .sup.1J.sub.C,P=91 Hz, .sup.2J.sub.C,F=17 Hz (1C.sup.a), 30.0° (1C.sup.d-h), 30.1° (1C.sup.d-h), 34.1 (1C.sup.i), 114.0 (1C.sup.l), 138.7 (1C.sup.k), n.b. (2C.sub.2F.sub.5)
[0344] .sup.19F NMR: −49.4 d, t, qui, sep .sup.1J.sub.F,P=875 Hz, .sup.3J.sub.F,H=17 Hz, .sup.3J.sub.F,F=14 Hz, .sup.4J.sub.F,F=11 Hz (2F), −82.7 t .sup.4J.sub.F,F=11 Hz (6F), −117.5 d, t .sup.2J.sub.F,P=111 Hz, .sup.3J.sub.F,F=14 Hz (4F)
[0345] .sup.31P NMR: −30.9 t, qui, t, t .sup.1J.sub.P,F=875 Hz, .sup.2J.sub.P,F=111 Hz, .sup.2J.sub.P,H=18 Hz, .sup.3J.sub.P,H=13 Hz (1P).
[0346] ° signals superimposed
EXAMPLE 13
Synthesis of bis(pentafluoroethyl)(undec-10-en-1-yl)-phosphine oxide by Reaction of bis(pentafluoroethyl)(undec-10-en-1-yl)difluorophosphorane and Hexamethyldisiloxane
[0347] ##STR00035##
[0348] The suspension from Example 12 consisting of bis(pentafluoroethyl)(undec-10-en-1-yl)difluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(C.sub.9H.sub.18CH═CH.sub.2) (7.48 mmol) in n-pentane (40 ml) (additionally contains bis(pentafluoroethyl)(cycloprop-8-yloctyl)difluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.2(C.sub.8H.sub.16-cyclo-C.sub.3H.sub.5) (4%) and ZnF2) is initially introduced in a 100 ml glass round-bottomed flask, and n-pentane is distilled off at 80° C. Hexamethyldisiloxane (2.32 g, 14.3 mmol) and water (2 g, 110 mmol) is subsequently added and stirred at room temperature for 45 minutes. A conversion of 88% to bis(pentafluoroethyl)(undec-10-en-1-yl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(C.sub.9H.sub.18CH═CH.sub.2), can be detected in the yellow mother liquor. By-products are bis(pentafluoroethyl)(cycloprop-8-yloctyl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(C.sub.8H.sub.16-cyclo-C.sub.3H.sub.5) (4 mol %), which results from bis(pentafluoroethyl)(cycloprop-8-yloctyl)difluorophosphorane in the starting material, and (pentafluoroethyl)(undec-10-en-1-yl)phosphinic acid, (C.sub.2F.sub.5)(C.sub.9H.sub.18CH═CH.sub.2)P(O)OH (8 mol %). In addition, undecene, ZnF.sub.2 and 1,21-docosadiene are also from the starting material (see Example 11). The compounds can be separated using methods which are known to the person skilled in the art. The suspension is used here without further purification. The product is characterised by means of .sup.1H, .sup.13C{.sup.1H}, .sup.19F and .sup.31P NMR spectra.
##STR00036##
[0349] NMR (lock substance: CD.sub.3CN film, δ in ppm) .sup.1H NMR: 1.28-1.30° s (8H.sup.d-g), 1.38° t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.h), 1.47 t, t .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=6 Hz, (2H.sup.c), 1.78 d, t, t .sup.3J.sub.H,P=10 Hz, .sup.3J.sub.H,H=8 Hz, .sup.3J.sub.H,H=8 Hz (2H.sup.b), 2.02 t, d, t, d .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz, .sup.4J.sub.H,H=1 Hz, .sup.4J.sub.H,H=1 Hz (2H.sup.i), 2.29 d, t .sup.2J.sub.H,P=11 Hz, .sup.3J.sub.H,H=8 Hz (2H.sup.a), 4.87 d, d, t, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=1 Hz, .sup.5J.sub.H,H=1 Hz (1H.sup.m), 4.94 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=2 Hz (1H.sup.l), 5.74 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H32 7 Hz (1H.sup.k) .sup.13C{.sup.1H} NMR: 20.1 d .sup.2J.sub.C,P=5 Hz (1C.sup.b), 24.1 d .sup.1J.sub.C,P=61 Hz (1C.sup.a), 29.1 d .sup.4J.sub.C,P=0.8 Hz (1C.sup.d), 29.2 (1C.sup.e-h), 29.6 (1C.sup.e-h), 30.0° (1C.sup.e-h), 30.1° (1C.sup.e-h), 30.9 d .sup.3J.sub.C,P=15 Hz (1C.sup.c), 34.1 (1C.sup.i), 112.9 t, m .sup.1J.sub.C,F=286 Hz (2CF.sub.2), 114.3 (1C.sup.l), 118.4 q, m .sup.1J.sub.C,F=287 Hz (2CF.sub.3), 138.6 (1C.sup.k)
[0350] .sup.19F NMR: −80.0 d .sup.3J.sub.F,P=3 Hz (6F), −121.5 d, m .sup.2J.sub.FA,P=75 Hz, .sup.2J.sub.FB,P=66 Hz, .sup.2J.sub.FA,FB=340 Hz (2F.sub.A), −123.5 d, m, .sup.2J.sub.FA′,P=75 Hz, .sup.2J.sub.FB′,P=66 Hz, .sup.2J.sub.FA′,FB′=310Hz (2F.sub.B)
[0351] .sup.31P NMR: 37.6 t, t, t, t .sup.2J.sub.P,FA=.sup.2J.sub.P,FA′=75 Hz, .sup.2J.sub.P,FB=.sup.2J.sub.P,FB′=66 Hz, .sup.2J.sub.P,H=11 Hz, .sup.3J.sub.P,H=10 Hz (1P).
[0352] ° signals superimposed
EXAMPLE 14
Synthesis of pentafluoroethyl(undec-10-en-1-yl)phosphinic acid by Hydrolysis of bis(pentafluoroethyl)(undec-10-en-1-yl)-phosphine oxide
[0353] ##STR00037##
[0354] Water (7 g, 390 mmol) is added to the suspension from Example 13, bis-(pentafluoroethyl)(undec-10-en-1-yl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)—(C.sub.9H.sub.18CH═CH.sub.2) [besides undecene, ZnF.sub.2 and 1,21-docosadiene, additionally contains bis(pentafluoroethyl)(cycloprop-8-yloctyl)phosphine oxide, (C.sub.2F.sub.5).sub.2P(O)(C.sub.8H.sub.16-C-C.sub.3H.sub.5) (4 mol %), and pentafluoroethyl(undec-10-en-1-yl)phosphinic acid, (C.sub.2F.sub.5)(C.sub.9H.sub.18CH═CH.sub.2)P(O)OH (8 mol %)], in a 250 ml glass round-bottomed flask and warmed (50° C.). This emulsion is stirred at 50° C. for 21 hours and at 100° C. for 1 hour. The emulsion is subsequently extracted with hot n-pentane (60 ml) and n-hexane (60 ml) under reflux. The organic phases are combined and washed with water (10 ml). All volatile constituents from the organic phase are removed at room temperature to 90° C. in vacuo (10.sup.−3 mbar). Pentafluoroethyl(undec-10-en-1-yl)-phosphinic acid, (C.sub.2F.sub.5)(C.sub.9H.sub.18CH═CH.sub.2)P(O)OH (2.32 g, 6.9 mmol), can be isolated as a yellow solid with a yield of 88%. By-products are pentafluoroethyl(cycloprop-8-yloctyl)phosphinic acid, (C.sub.2F.sub.5)(C.sub.8H.sub.16-cyclo-C.sub.3H.sub.5)P(O))OH (4%), and 1,21-docosadiene from Example 12. The compounds can be removed using methods which are known to the person skilled in the art. The product is characterised by means of .sup.1H, .sup.13C{.sup.1H}, .sup.19F and .sup.31P NMR spectra.
##STR00038##
[0355] NMR (lock substance: toluene-d8; δ in ppm) .sup.1H NMR: 1.27-1.32° s (10H.sup.c-g), 1.36° t .sup.3J.sub.H,H=7 Hz (2H.sup.h), 1.83*° s (2H.sup.b), 1.99° t, d, t, .sup.3J.sub.H,H=7 Hz, .sup.3J.sub.H,H=7 Hz, .sup.4J.sub.H,H=1 Hz (2H.sup.i), 2.05*° d, t .sup.2J.sub.H,P=12 Hz, .sup.3J.sub.H,H=7 Hz (2H.sup.a), 4.97 d, d, t .sup.3J.sub.H,H=10 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=1 Hz (1H.sup.m), 5.02 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.2J.sub.H,H=2 Hz, .sup.4J.sub.H,H=2 Hz (1H.sup.l), 5.78 d, d, t .sup.3J.sub.H,H=17 Hz, .sup.3J.sub.H,H=10 Hz, .sup.3J.sub.H,H=7 Hz (1H.sup.k), 13.01 s (.sup.1H.sup.n)
[0356] .sup.13C{.sup.1H} NMR: 23.6* (1C.sup.b), 25.9* d .sup.1J.sub.C,P=103 Hz (1C.sup.a), 29.8° d .sup.4J.sub.C,P=0.9 Hz (1C.sup.d), 29.8° (1C.sup.e-h), 29.9 (1C.sup.e-h), 30.1 (1C.sup.e-h), 30.3 (1C.sup.e-h), 31.2 d .sup.3J.sub.C,P=16 Hz (1C.sup.c), 34.7 (1C.sup.i), 114.9 (1C.sup.l), 139.5 (1C.sup.k), n.b. (1C.sub.2F.sub.5)
[0357] .sup.19F NMR: −80.5 s (3F), −127.3 d .sup.2J.sub.F,P=79 Hz (2F)
[0358] .sup.31P NMR: −35.7 t, t, t .sup.2J.sub.P,F=79 Hz, .sup.2J.sub.P,H=12 Hz, .sup.3J.sub.P,H=12 Hz (1P).
[0359] * signals broadened
[0360] ° signals superimposed
EXAMPLE 15
Synthesis of 4-styrylmagnesium Chloride by Reaction of 4-chlorostyrene and Magnesium
[0361] ##STR00039##
[0362] Magnesium turnings (1.78 g, 73.2 mmol) are suspended in tetrahydrofuran (20 ml) in a 100 ml glass round-bottomed flask and activated using bromoethane, C.sub.2H.sub.5Br (1.16 g, 10.6 mmol). After 10 minutes, the THF mother liquor is decanted. The activated magnesium turnings (1.52 g, 62.6 mmol) are re-suspended in THF (60 ml), 4-chlorostyrene (7.24 g, 52.2 mmol) is added and warmed (70° C.). After 1 hours at 70° C., a brown-black suspension can be obtained. The conversion to 4-styrylmagnesium chloride is 98%. The brown-black THF mother liquor can be stored cooled (0° C.) for some time. The product is characterised by .sup.1H and .sup.13C NMR spectra.
##STR00040##
[0363] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 4.96 d, d .sup.3J.sub.H,H=11 Hz, .sup.2J.sub.H,H=1.6 Hz (1H.sup.g), 5.62 d, d .sup.3J.sub.H,H=18 Hz, .sup.2J.sub.H,H=1.6 Hz (1H.sup.f), 6.62 d, d .sup.3J.sub.H,H=18 Hz, .sup.3J.sub.H,H=11 Hz (1H.sup.e), 7.10 d .sup.3J.sub.H,H=8 Hz (2H.sup.c), 7.71 d .sup.3J.sub.H,H=8 Hz (2H.sup.b)
[0364] .sup.13C NMR: 108.7 d, d .sup.1J.sub.C,H=159 Hz, .sup.1J.sub.C,H=154 Hz (1C.sup.f), 123.4 d, d, d, d, m .sup.1J.sub.C,H=151 Hz, .sup.3J.sub.C,H=5 Hz, .sup.3J.sub.C,H=4 Hz, .sup.4J.sub.C,H=4 Hz (2C.sup.c), 133.1 m (1C.sup.d), 139.6 d, t, d, m .sup.1J.sub.C,H=150 Hz, .sup.3J.sub.C,H=5 Hz, .sup.2J.sub.C,H=3 Hz (1C.sup.e), 140.8 d, d, m .sup.1J.sub.C,H=151 Hz, .sup.2J.sub.C,H=12 Hz (2C.sup.b), 172.2 m (1C.sup.a).
EXAMPLE 16
Synthesis of di(4-styryl)zinc by Reaction of 4-styrylmagnesium Chloride and Zinc Chloride
[0365] ##STR00041##
[0366] 4-Styrylmagnesium chloride (51.2 mmol) in tetrahydrofuran (60 ml) from Example 15 is initially introduced in a 100 ml glass round-bottomed flask and cooled (0° C.). Zinc chloride, ZnCl.sub.2 (3.35 g, 24.6 mmol), is added to this THF solution. The suspension is stirred at 0° C. for 2.5 hours and subsequently centrifuged. The yellow mother liquor is decanted into a 100 ml glass round-bottomed flask and THF is condensed off at 0° C. in vacuo (10.sup.−3 mbar). A white solid remains behind. This is extracted three times with toluene (50 ml each time). Toluene is condensed off from the combined toluene phases at 0° C. in vacuo (10.sup.−3 mbar) in a 250 ml glass round-bottomed flask. Since THF can still be detected in the resultant white solid, the solid is suspended two further times in toluene (20 ml each time). All volatile compounds are subsequently condensed off again at 0° C. in vacuo (10.sup.−3 mbar). Distyrylzinc-3THF (6.84 g, 14.0 mmol) can be isolated as a white solid with a yield of 57%. The isolated product is characterised by means of .sup.1H and .sup.13C NMR spectra.
##STR00042##
[0367] NMR (lock substance: CD.sub.3CN; δ in ppm) .sup.1H NMR: 5.11 d .sup.3J.sub.H,H=11 Hz (2H.sup.g), 5.73 d
[0368] .sup.3J.sub.H,H=18 Hz (2H.sup.f), 6.71 d, d .sup.3J.sub.H,H=18 Hz, .sup.3J.sub.H,H=11 Hz (2H.sup.e), 7.25 d .sup.3J.sub.H,H=8 Hz (4H.sup.c), 7.59 d .sup.3J.sub.H,H=8 Hz (4H.sup.b)
[0369] .sup.13C NMR: 111.7 d, d .sup.1J.sub.C,H=159 Hz, .sup.1J.sub.C,H=155 Hz (2C.sup.f), 125.0 d .sup.1J.sub.C,H=153 Hz (4C.sup.c), 133.9 m (2C.sup.d), 139.2 d .sup.1J.sub.C,H=152 Hz (2C.sup.e), 139.6 d, d .sup.1J.sub.C,H=156 Hz, .sup.2J.sub.C,H=11 Hz (4C.sup.b), 160.5 m (2C.sup.a).
EXAMPLE 17
Synthesis of pentafluoroethyl)tetrafluorophosphorane
[0370] ##STR00043##
[0371] Pale-yellow hexylmethylimidazolium pentafluoroethylpentafluorophosphate, [C.sub.6MIM][C.sub.2F.sub.5PF.sub.5] (10.52 g, 25.52 mmol), is initially introduced in a 10 ml glass reactor with J. Young tap, cooled (−78° C.), and antimony pentafluoride, SbF.sub.5 (6.88 g, 31.74 mmol) is added. The reaction solution is warmed (RT), during which an emulsion forms. After 1.5 h at RT, pentafluoroethyltetrafluorophosphorane, C.sub.2F.sub.5PF.sub.4, is formed quantitatively as a very volatile clear and colourless liquid. The product is used directly without purification for subsequent experiments. Isolated product can be characterised by means of .sup.19F and .sup.31P NMR spectra.
##STR00044##
[0372] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.19F NMR: −60.1 d, t, q .sup.1J.sub.F,P=1090 Hz, .sup.3J.sub.F,F=8 Hz, .sup.4J.sub.F,F=6 Hz (4F), −84.7 qui, d .sup.4J.sub.F,F=6 Hz, .sup.3J.sub.F,P=4 Hz (3F), −120.7 d, qui .sup.2J.sub.F,P=125 Hz, .sup.3J.sub.F,F=8 Hz (2F)
[0373] .sup.31P NMR: −61.2 qui, t .sup.1J.sub.P,F=1091 Hz, .sup.2J.sub.P,F=125 Hz (1P).
EXAMPLE 18
Synthesis of pentafluoroethyl-(4-styryl)trifluorophosphorane by Reaction of di(4-styryl)zinc and pentafluoroethyltetrafluorophosphorane
[0374] ##STR00045##
[0375] Di(4-styryl)zinc-3THF (6.60 g, 13.5 mmol) is suspended in n-pentane (100 ml) in a 250 ml glass round-bottomed flask with subsequent cooled (−80° C.) condenser and cooled (0° C.). Pentafluoroethyltetrafluorophosphorane, C.sub.2F.sub.5PF.sub.4 (5.06 g, 22.4 mmol), is condensed into this suspension over the course of 15 minutes. The yellow suspension is stirred at 0° C. for a further 15 min and, when conversion is complete, warmed to room temperature. The suspension is subsequently centrifuged, and the pink-coloured mother liquor is decanted. The yield of pentafluoroethyl-(4-styryl)trifluorophosphorane, C.sub.2F.sub.5PF.sub.3(C.sub.6H.sub.4CH═CH.sub.2), in n-pentane is 49%. The product is characterised in n-pentane by means of .sup.1H, .sup.13C, .sup.19F and .sup.31P NMR spectra.
##STR00046##
[0376] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H NMR: 5.41 d .sup.3J.sub.H,H=11 Hz (1H.sup.9), 5.88 d .sup.3J.sub.H,H=18 Hz (1H.sup.f), 6.70 d, d .sup.3J.sub.H,H=18 Hz, .sup.3J.sub.H,H=11 Hz (1H.sup.e), 7.47 d, d .sup.3J.sub.H,H=8 Hz, .sup.4J.sub.H,P=6 Hz (2H.sup.c), 8.04 d, d, m .sup.3J.sub.H,P=15 Hz, .sup.3J.sub.H,H=8 Hz (2H.sup.b)
[0377] .sup.13C NMR: 118.5 d, d .sup.1J.sub.C,H=162 Hz, .sup.1J.sub.C,H=155 Hz (1C.sup.f), 127.3 d, d, d, d .sup.1J.sub.C,H=161 Hz, .sup.3J.sub.C,P=19 Hz, .sup.2J.sub.C,H6 Hz, .sup.3J.sub.C,H=6 Hz (2C.sup.c), 136.0 d, m .sup.1J.sub.C,H=157 Hz (1C.sup.e), 138.8 d, d, q, m .sup.1J.sub.C,H=166 Hz, .sup.2J.sub.C,P=15 Hz, .sup.3J.sub.C,F=7 Hz (2C.sup.b), 145.8 m (1C.sup.d), n.d. (1C.sup.a), n.d. (1C.sub.2F.sub.5)
[0378] .sup.19F NMR: −70.5* s (3F), −82.3 t, d, q .sup.4J.sub.F,F=7 Hz, .sup.3J.sub.F,P=7 Hz, .sup.3J.sub.F,F=2 Hz (3F), −118.6 d, q, q .sup.2J.sub.F,P=116 Hz, .sup.3J.sub.F,F=12 Hz, .sup.3J.sub.F,f=2 Hz (2F)
[0379] .sup.31P NMR: −40.5 q, t, t, t, .sup.1J.sub.P,F=965 Hz, .sup.2J.sub.P,F=116 Hz, .sup.3J.sub.P,H=15 Hz, .sup.4J.sub.P,H=6 Hz (1P).
[0380] * signals broadened
EXAMPLE 19
Synthesis of pentafluoroethyl-(4-styryl)phosphinic acid by Hydrolysis of pentafluoroethyl-(4-styryl)trifluorophosphorane using Hexamethyldisiloxane and Water
[0381] ##STR00047##
[0382] Hexamethyldisiloxane (7.35 g, 45.3 mmol) and water (1.02 g, 56.6 mmol) are added to pentafluoroethyl-(4-styryl)trifluorophosphorane, (C.sub.2F.sub.5)-(4-C.sub.6H.sub.4CH═CH.sub.2)PF.sub.3 (11.2 mmol), in n-pentane (100 ml) from Example 18 in a 250 ml glass round-bottomed flask. A colourless emulsion resulted. After 2.5 hours at room temperature, the upper n-pentane phase contained neither (C.sub.2F.sub.5)(4-C.sub.6H.sub.4CH═CH.sub.2)PF.sub.3 nor product. The n-pentane phase was decanted, the lower phase was suspended in water (10 ml) and washed twice with n-pentane (10 ml each time). The small proportion of solid is filtered off and all volatile constituents of the mother liquor are condensed off at room temperature in vacuo (10.sup.−3 mbar). Pentafluoroethyl-(4-styryl)phosphinic acid, (C.sub.2F.sub.5)(CH.sub.2═CH—C.sub.6H.sub.4)P(O)OH.Math.0.5H.sub.2O (3.32 g, 11.2 mmol), can be isolated as a beige tacky solid with quantitative yield. The isolated product is characterised by means of .sup.1H and .sup.13C NMR spectra.
##STR00048##
[0383] NMR (lock substance: CD.sub.3CN; δ in ppm) .sup.1H NMR: 5.49 d .sup.3J.sub.H,H=11 Hz (1H.sup.g), 6.00 d .sup.3J.sub.H,H=18 Hz (1H.sup.f), 6.83 d, d .sup.3J.sub.H,H=18 Hz, .sup.3J.sub.H,H=11 Hz (1H.sup.e), 7.63 d, d .sup.3J.sub.H,H=8 Hz, .sup.4J.sub.H,P=4 Hz (2H.sup.c), 7.84 d, d, m .sup.3J.sub.H,P=13 Hz, .sup.3J.sub.H,H=8 Hz (2H.sup.b), 9.51 s (OH)
[0384] .sup.13C NMR: 112.6 t, d, q .sup.1J.sub.C,F=276.6 Hz, .sup.1J.sub.C,P=136.7 Hz, .sup.2J.sub.C,F=38.7 Hz (1CF.sub.2), 118.8 d, d .sup.1J.sub.C,H=161 Hz, 1J.sub.C,H=155 Hz (1C.sup.f), 120.0 q, t, d .sup.1J.sub.C,F=285.9 Hz, .sup.2J.sub.C,F=31.1 Hz, .sup.2J.sub.C,P=16.5 Hz (1CF.sub.3), 124.9 d, t, m .sup.1J.sub.C,P=150.8 Hz, .sup.3J.sub.C,H=7.6 Hz (1C.sup.a) 127.6 d, d, d, d, m .sup.1J.sub.C,H=161.5 Hz, .sup.3J.sub.C,P=14.7 Hz, .sup.2J.sub.C,H=5.8 Hz, .sup.3J.sub.C,H=5.6 Hz (1C.sup.c), 134.5 d, d, d, m .sup.1J.sub.C,H=167.0 Hz, 2J.sub.C,P=11.1 Hz, .sup.2J.sub.C,H=6.8 Hz (1C.sup.b), 136.6 d, d, d, d, m .sup.1J.sub.C,H=156.9 Hz, .sup.3J.sub.C,H=4.4 Hz, .sup.3J.sub.C,H=4.4 Hz, .sup.5J.sub.C,P=1.5 Hz (1C.sup.e), 144.6 m (1C.sup.d) .sup.19F NMR: −80.9 t, d .sup.3J.sub.F,F=1.8 Hz, .sup.3J.sub.F,P=1.0 Hz (3F), −127.1 d, q .sup.2J.sub.F,P=80.0 Hz, .sup.3J.sub.F,F=1.8 Hz (2F)
[0385] .sup.31P NMR: 17.5 t, t, t .sup.2J.sub.P,F=79.9 Hz, .sup.3J.sub.P,H=12.4 Hz, .sup.4J.sub.P,H=3.7 Hz (1P).
EXAMPLE 20
Synthesis of bis(pentafluoroethyl)difluoro-3,4,4-trifluorobut-3-en-1-ylphosphorane from bis(pentafluoroethyl)trifluorophosphorane and 3,4,4-trifluorobut-3-en-1-ylmagnesium bromide
[0386] ##STR00049##
[0387] A cold (−50° C.) yellow diethyl ether solution of 3,4,4-trifluorobut-3-en-1-ylmagnesium bromide, CF.sub.2═CFCH.sub.2CH.sub.2MgBr (33 mmol in 50 ml, additionally contains 1,1,2,7,8,8-hexafluorocta-1,7-diene and 1,1,2-trifluorobut-1-ene), is reacted with bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3 (9.40 g, 28.8 mmol), in a 100 ml glass round-bottomed flask. A white solid precipitates out. The suspension is stirred at −50° C. to −40° C. for 1 hour. The reaction suspension is subsequently filtered at −30° C., the solid is washed with diethyl ether (5 ml) and subsequently condensed over at RT in vacuo (10.sup.−3 mbar). Bis(pentafluoroethyl)difluoro-3,4,4-trifluorobut-3-en-1-ylphosphorane, (C.sub.2F.sub.5).sub.2(CF.sub.2═CFCH.sub.2CH.sub.2)PF.sub.2 (17.4 mmol), can be isolated as a clear and colourless diethyl ether solution with a yield of 60%.
##STR00050##
[0388] NMR (lock substance: CD.sub.3CN film; δ in ppm) .sup.1H-NMR: 2.70 d, d, m .sup.3J.sub.H,F=20 Hz, .sup.3J.sub.H,P=18 Hz (2H.sup.b), 2.89 d, m .sup.2J.sub.H,P=18 Hz (2H.sup.a).
[0389] .sup.19F-NMR: −49.1 d, t, q, m .sup.1J.sub.F,P=880 Hz, .sup.3J.sub.F,F=14 Hz, .sup.4J.sub.F,F=10 Hz (2F), −82.6 t .sup.4J.sub.F,F=10 Hz (6F), −105.4 d, d, t, m .sup.2J.sub.F,F=83 Hz, .sup.3J.sub.F,F=34 Hz, .sup.4J.sub.F,H=3 Hz (1F.sup.e), −117.4 d, t .sup.2J.sub.F,P=113 Hz, .sup.3J.sub.F,F=14 Hz (4F), −123.6 d, d, t, m .sup.3J.sub.F,F=115 Hz, .sup.2J.sub.F,F=83 Hz, .sup.4J.sub.F,H=3 Hz (1F.sup.d), −179.3 d, d, t, m .sup.3J.sub.F,F=115 Hz, .sup.3J.sub.F,F=34 Hz, .sup.3J.sub.F,H=20 Hz (1F.sup.c).
[0390] .sup.31P-NMR: −31.5 t, qui, t, t .sup.1J.sub.P,F=880 Hz, .sup.2J.sub.P,F=113 Hz, .sup.2J.sub.P,H=18 Hz, .sup.3J.sub.P,H=18 Hz (1P).
EXAMPLE 21
Synthesis of bis(pentafluoroethyl)-3,4,4-trifluorobut-3-en-1-ylphosphine oxide by Reaction of bis(pentafluoroethyl)difluoro-3,4,4-trifluorobut-3-en-1-ylphosphorane and Hexamethyldisiloxane with Catalytic Amounts of H.SUB.2.O
[0391] ##STR00051##
[0392] A clear and colourless ether solution with bis(pentafluoroethyl)difluoro-3,4,4-trifluorobut-3-en-1-ylphosphorane, (C.sub.2F.sub.5).sub.2(CF.sub.2═CFCH.sub.2CH.sub.2)PF.sub.2 (17.4 mmol, additionally contains 1,1,2,7,8,8-hexafluorocta-1,7-diene and 1,1,2-trifluorobut-1-ene), from Example 1 is stirred with hexamethyldisiloxane, ((CH.sub.3).sub.3Si).sub.2O (5.75 g, 35.4 mmol), and water (2 mg, 0.11 mmol) at RT for 0.5 hours in a 100 ml glass round-bottomed flask with evolution of gas. The volatile constituents are removed at −40 to −10° C. in vacuo (10.sup.−3 mbar). Bis(pentafluoroethyl)-3,4,4-trifluorobut-3-en-1-ylphosphine oxide (6.42 g, 16.3 mmol) can be isolated as a pale-yellow liquid with a yield of 94% and a purity of 99%.
##STR00052##
[0393] NMR (lock substance: CDCl.sub.3; δ in ppm) .sup.1H-NMR: 2.57 d, t .sup.2J.sub.H,P=10 Hz, .sup.3J.sub.H,H=6 Hz (2H.sup.a), 2.77 d, d, t, d, d .sup.3J.sub.H,F=19 Hz, .sup.3J.sub.H,P=19 Hz, .sup.3J.sub.H,H=6 Hz, .sup.4J.sub.H,F=3 Hz, .sup.4J.sub.H,F=3 Hz (2H.sup.b).
[0394] .sup.13C-NMR: 17.5 t, d, m .sup.1J.sub.C,H=133 Hz, .sup.2J.sub.C,P=23 Hz (1C.sup.b), 20.5 t, d, m .sup.1J.sub.C,H=132 Hz, .sup.1J.sub.C,P=62 Hz (1C.sup.a), 112.8 d, d, d, q, m .sup.1J.sub.C,F.sub.
[0395] .sup.19F-NMR: −80.9 m (6F), −104.3 d, d, t .sup.2J.sub.F,F=83 Hz, .sup.3J.sub.F,F=33 Hz, .sup.4J.sub.F,H=3 Hz (1F.sup.e), −122.1 d, m .sup.2J.sub.FA,FB=340 Hz (2F.sub.A), .sup.2J.sub.F.sub.
[0396] .sup.31P-NMR: 36.1 t, t, t, t .sup.2J.sub.P,F.sub.
EXAMPLE 22
Synthesis of pentafluoroethyl-3,4,4-trifluorobut-3-en-1-ylphosphinic acid by Hydrolysis of bis(pentafluoroethyl)-3,4,4-trifluorobut-3-en-1-ylphosphine oxide
[0397] ##STR00053##
[0398] Pale-yellow bis(pentafluoroethyl)-3,4,4-trifluorobut-3-en-1-ylphosphine oxide, (C.sub.2F.sub.5).sub.2(CF.sub.2═CFCH.sub.2CH.sub.2)P═O (5.75 g, 14.6 mmol) from Example 2, is emulsified in water (5 ml) in a 25 ml glass round-bottomed flask and warmed (50° C.). The emulsion is stirred at 50° C. for 4 h. All volatile constituents are subsequently removed at RT to 50° C. in vacuo (10.sup.−3 mbar). Pentafluoroethyl-3,4,4-trifluorobut-3-en-1-ylphosphinic acid (4.12 g, 14.1 mmol) can be isolated as a pale-yellow liquid with a yield 97% and a purity of 99%.
##STR00054##
[0399] NMR (lock substance: CDCl.sub.3; δ in ppm) .sup.1H-NMR: 2.25 d, t .sup.2J.sub.H,P=13 Hz, .sup.3J.sub.H,H=8 Hz (2H.sup.a), 2.72 d, d, t, d, d .sup.3J.sub.H,F=20 Hz, .sup.3J.sub.H,P=12 Hz, .sup.3J.sub.H,H=8 Hz, .sup.4J.sub.H,F=4 Hz, .sup.4J.sub.H,F=2 Hz (2H.sup.b), 13.26 s Δv.sub.1/2=2 Hz (1OH).
[0400] .sup.13C-NMR: 17.8 t, d, m .sup.1J.sub.C,H=133 Hz, .sup.2J.sub.C,P=23 Hz (1C.sup.b), 21.8 t, d, m .sup.1J.sub.C,H=131 Hz, .sup.1J.sub.C,P=104 Hz (1C.sup.a), 111.1 t, d, q, m .sup.1J.sub.C,F=277 Hz, .sup.1J.sub.C,P=133 Hz, .sup.2J.sub.C,F=40 Hz (CF.sub.2), 118.5 q, t, d, m .sup.1J.sub.C,F=286 Hz, .sup.2J.sub.C,F=31 Hz, .sup.2J.sub.C,P=17 Hz (CF.sub.3), 126.7 d, d, d, d, m .sup.1J.sub.C,F=235 Hz, .sup.2J.sub.C,F=53 Hz, .sup.2J.sub.C,F=17 Hz .sup.3J.sub.C,P=16 Hz (1C.sup.c), 153.0 d, d, d, t .sup.1J.sub.C,F=288 Hz, .sup.1J.sub.C,F=275 Hz, .sup.2J.sub.C,F=46 Hz, .sup.3J.sub.C,H=3 Hz (1C.sup.d).
[0401] .sup.19F-NMR: −80.7 s Δv.sub.1/2=4 Hz (3F), −103.0 d, d, t, m .sup.2J.sub.F,F=83 Hz, .sup.3J.sub.F,F=33 Hz, .sup.4J.sub.F,H=2 Hz (1F.sup.e), −121.9 d, d, t .sup.3J.sub.F,F=115 Hz, .sup.2J.sub.F,F=83 Hz, .sup.4J.sub.F,H=4 Hz (1F.sup.d), −127.3 d .sup.2J.sub.F,P=84 Hz (2F), −176.9 d, d, t .sup.3J.sub.F,F=115 Hz, .sup.3J.sub.F,F=33 Hz, .sup.3J.sub.F,H=20 Hz (1F.sup.c).
[0402] .sup.31P-NMR: 33.8 t, t, t .sup.2J.sub.P,F=84 Hz, .sup.2J.sub.P,H=13 Hz, .sup.3J.sub.P,H=12 Hz (1P).
EXAMPLE 23
Synthesis of bis(pentafluoroethyl)difluoro-1,2,2-trifluorovinylphosphorane from bis(pentafluoroethyl)trifluorophosphorane and 1,2,2-trifluorovinylzinc chloride
[0403] ##STR00055##
[0404] A cold (0° C.) dark-brown solution of trifluorovinylzinc chloride, CF.sub.2═CFZnCl (795 mg; 4.37 mmol, additionally contains 1.46 mmol of Et.sub.2O and 2.24 mmol of C.sub.6H.sub.5CF.sub.3 as internal standard), in toluene (10 ml) is reacted with bis(pentafluoroethyl)trifluorophosphorane, (C.sub.2F.sub.5).sub.2PF.sub.3 (1.46 g; 4.48 mmol), over the course of 15 min In a 25 ml glass round-bottomed flask. The conversion to (C.sub.2F.sub.5).sub.2(CF.sub.2═CF)PF.sub.2 (714 mg; 1.84 mmol) is calculated as 42% with the aid of the internal standard. The brown-black suspension is firstly condensed over at RT and the condensate is subsequently condensed over at −40° C. to −25° C. in vacuo (10.sup.−3 mbar). The resultant colourless condensate contains the product in toluene (10 ml) and 1.72 mmol of C.sub.6H.sub.5CF.sub.3. This clear and colourless liquid is used without further purification.
##STR00056##
[0405] NMR (lock substance: CD.sub.3CN; δ in ppm)
[0406] .sup.19F-NMR: −55.8 d, d, qui, d, hep, d .sup.1J.sub.F,P=920 Hz, .sup.4J.sub.F,F=54 Hz, .sup.3J.sub.F,F=14 Hz, .sup.4J.sub.F,F=11 Hz, .sup.4J.sub.F,F=9 Hz, .sup.3J.sub.F,F=5 Hz (2F), −58.8 d, d, d, t .sup.3J.sub.F,F=40 Hz, .sup.3J.sub.F,P=22 Hz, .sup.2J.sub.F,F=17 Hz, .sup.4J.sub.F,F=11 Hz (1F.sup.a), −81.6 d, t, d, d .sup.3J.sub.F,F=113 Hz, .sup.4J.sub.F,F=54 Hz, .sup.2J.sub.F,F=17 Hz, .sup.3J.sub.F,P=16 Hz (1F.sup.b), −82.4 t .sup.4J.sub.F,F=9 Hz (6F), −117.2 d, t .sup.2J.sub.F,P=120 Hz, .sup.3J.sub.F,F=14 Hz (4F), −185.5 d, d, d, t .sup.3J.sub.F,F=113 Hz, 2J.sub.F,P=83 Hz, .sup.3J.sub.F,F=40 Hz, .sup.3J.sub.F,F=5 Hz (1F.sup.c).
[0407] .sup.31P-NMR: −54.1 t, qui, d, d, d .sup.1J.sub.P,F=920 Hz, .sup.2J.sub.P,F=120 Hz, .sup.2J.sub.P,F=83 Hz, .sup.3J.sub.P,F=22 Hz, .sup.3J.sub.P,F=16 Hz (1P).
EXAMPLE 24
Synthesis of bis(pentafluoroethyl)(1,2,2-trifluorovinyl)phosphine oxide from bis(pentafluoroethyl)difluoro-1,2,2-trifluorovinylphosphorane and Hexamethyldisiloxane
[0408] ##STR00057##
[0409] A colourless solution of bis(pentafluoroethyl)difluorotrifluorovinylphosphorane, (C.sub.2F.sub.5).sub.2(CF.sub.2═CF)PF.sub.2(714 mg; 1.84 mmol), in toluene (10 ml, contains 1.72 mmol of C.sub.6H.sub.5CF.sub.3 as internal standard) from Example 4 is reacted with hexamethyldisiloxane, ((CH.sub.3).sub.3Si).sub.2O (620 mg; 3.82 mmol) in a 25 ml glass round-bottomed flask. The reaction solution is stirred at RT for 30 min. After 30 min at RT, the conversion is quantitative. The amount of bis(pentafluoroethyl)trifluorovinylphosphine oxide (655 mg, 1.79 mmol) is determined with the aid of the internal standard, and the solution is used without further purification.
##STR00058##
[0410] NMR (lock substance: CD.sub.3CN; δ in ppm) .sup.19F-NMR: −63.6 d, d, d .sup.3J.sub.F,F=29 Hz, .sup.3J.sub.F,P=11 Hz (1F.sup.a), 2J.sub.F,F=7 Hz, −80.4 s Δv.sub.1/2=6 Hz (6F), −93.7 d, d, d .sup.3J.sub.F,F=121 Hz, .sup.3J.sub.F,P=15 Hz, .sup.2J.sub.F,F=7 Hz (1F.sup.b), −121.1 d, m .sup.2J.sub.F.sub.
[0411] .sup.31P-NMR: 7.7 t, t, d, d, d .sup.2J.sub.P,F.sub.
EXAMPLE 25
Synthesis of pentafluoroethyl-1,2,2-trifluorovinylphosphinic acid from bis(pentafluoroethyl)(1,2,2-trifluorovinyl)phosphine oxide and Water
[0412] ##STR00059##
[0413] A colourless solution of bis(pentafluoroethyl)trifluorovinylphosphine oxide, (C.sub.2F.sub.5).sub.2(CF.sub.2═CF)P═O(655 mg, 1.79 mmol), in toluene (10 ml, also contains C.sub.6H.sub.5CF.sub.3, ((CH.sub.3).sub.3Si).sub.2O and (CH.sub.3).sub.3SiF) is emulsified in water (15 ml) in a 25 ml glass round-bottomed flask and warmed (50° C.). The emulsion is stirred at 50° C. for 3 h. After 3 h at RT, the conversion is quantitative. All volatile constituents are removed at RT in vacuo (10.sup.−3 mbar). Pentafluoroethyltrifluorovinylphosphinic acid (410 mg, 1.76 mmol) can be isolated as a colourless liquid with the yield of 98%.
##STR00060##
[0414] NMR (solvent: CD.sub.3CN; δ in ppm) .sup.1H-NMR: 13.00 s Δv.sub.1/2=7 Hz (1OH)
[0415] .sup.19F-NMR: −75.9 d, d, d .sup.3J.sub.F,F=30 Hz, .sup.2J.sub.F,F=24 Hz, .sup.3J.sub.F,P=15 Hz (1F.sup.a), −81.9 s Δv.sub.1/2=6 Hz (3F), −97.4 d, d, d .sup.3J.sub.F,F=120 Hz, .sup.2J.sub.F,F=24 Hz, .sup.3J.sub.F,P=15 Hz (1F.sup.b), −128.9 d .sup.2J.sub.F,R=90 Hz (2F), −195.0 d, d, d .sup.3J.sub.F,F=120 Hz, .sup.2J.sub.F,P=65 Hz, .sup.3J.sub.F,F=30 Hz (1F.sup.c)
[0416] .sup.31P-NMR: 0.6 t, d, d, d .sup.2J.sub.P,F=90 Hz, .sup.2J.sub.P,F=65 Hz, .sup.3J.sub.P,F=15 Hz, .sup.3J.sub.P,F=15 Hz (1P).
EXAMPLE 26
Polymerisation of pentafluoroethyl-(4-styryl)phosphinic acid with AIBN
[0417] ##STR00061##
[0418] Pentafluoroethyl-(4-styryl)phosphinic acid, (C.sub.2F.sub.5)(4-styryl)P(O)OH.Math.0.5H.sub.2O (1.12 g; 3.79 mmol) is dissolved in CH.sub.3CN (20 ml) with azobisisobutyronitrile (AIBN)(50 mg; 0.30 mmol) in a 25 ml glass round-bottomed flask with vigorous stirring and warmed (75° C.). Cloudiness can immediately be observed. After 1.5 h at 75° C., the milky-cloudy suspension is transferred into a 100 ml glass round-bottomed flask with CH.sub.3CN (5 ml). All volatile substances are removed at RT in vacuo (10.sup.−3 mbar), and the white pulverulent solid is dried for a further 2 h. Polymeric material can be isolated as a white powder with a yield of 96%. The polymer also contains 0.3 equivalent of CH.sub.3CN and 0.1 equivalent of H.sub.2O (elemental analysis) and also about 5 mol % of unpolymerised (C.sub.2F.sub.5)(4-styryl)P(O)OH(NMR). The average degree of polymerisation (351600 formula units) was determined via the weight average molecular weight and the polydispersity by means of GPC.
[0419] Impurities, such as CH.sub.3CN, can be removed on drying (50-60° C.) in a high vacuum for 1 day.
[0420] Analytical Result (GPC):
TABLE-US-00001 Mw Mp D Poly(pentafluoroethyl-4- 94,522,300 5,143,990 4,338.20 styrylphosphinic acid) 100,648,000 5,179,390 2,905.77 Notes: entire polymer distribution evaluated
TABLE-US-00002 Mw Mp D Poly(pentafluoroethyl-4- 17,487,700 5,143,990 2.92 styrylphosphinic acid) 17,387,700 5,179,390 2.80 Notes: only maximum evaluated
[0421] Mw is the weight average molecular weight, calculated over the entire peak.
[0422] Mp is the molecular weight at the peak maximum.
[0423] D (polydispersity) is an indication of the width of the weight distribution of the peak. The higher this value, the broader the weight distribution. [0424] The analysis shows a very broad weight distribution with a maxima at ˜5,200,000 Da.
[0425] The following experiment demonstrates the applicability thereof.
[0426] Determination of the Ion Exchange Capacity (IEC):
[0427] The polymer [(C.sub.2F.sub.5)(4-styryl)P(O)OH].sub.n (214 mg; 0.748 mmol) is suspended in 0.1 M NaOH.sub.(aq) (10 ml, titre: 1.0019) in a glass round-bottomed flask (25 ml) and stirred vigourously at RT for 24 h. The resultant solution is titrated with 0.1 M HCl.sub.(aq) (titre: 1.0185). The consumption of 0.1 M HCl.sub.(aq) at the equivalence point is 2.752 ml. Taking into account the titre, this results in an amount of 0.720 mmol of acidic protons in the polymeric material. A value of 3.36 meq/g (theor.: 3.49 meq/g) thus arises for the IEC. Taking into account the impurities, such as CH.sub.3CN, the measured ion exchange capacity IEC of the polymer is >99% of the theoretical value.
EXAMPLE 27
Extraction of Europium Chloride using polypentafluoroethyl-4-styrylphosphinic acid
[0428] ##STR00062##
[0429] Polypentafluoroethyl-4-styrylphosphinic acid, [(C.sub.2F.sub.5)(4-styryl)-P(O)OH.Math.0.5H.sub.2O].sub.n (210 mg; 0.712 mmol), is added to a solution of EuCl.sub.3 (159 mg; 0.616 mmol) in H.sub.2O (2 ml) in an FEP reactor (Ø.sub.i=8 mm), and the mixture is stirred at RT. After 20 h, the pale-yellow suspension with fine precipitate (A) is centrifuged, the mother liquor is decanted and the white solid (A) is washed with H.sub.2O (3×2 ml). The combined mother liquors are evaporated at RT in vacuo (10.sup.−3 mbar), and the resultant white and solid residue (B) (157 mg) is dried at RT in vacuo (10.sup.−3 mbar) for a further 5 h. The white solid (B) fluoresced intensely red (EuCl.sub.3) on irradiation with UV light (λ=366 nm). The water content of the solid was determined as 45 mg (2.5 mmol) by means of Karl Fischer titration. Elemental analysis of the solid shows little contamination by CH.sub.3CN (3 mg; 0.07 mmol) from the starting material. No chloride was detected in the polymer (A) by X-ray fluorescence analysis. The ratio of europium to phosphorus is 0.30 to 1.00. EuCl.sub.3 (157 mg−45 mg (H.sub.2O)−3 mg (CH.sub.3CN)=109 mg (0.422 mmol)) can be recovered as white solid (A). Eu.sup.3+ (0.194 mmol) in the polymer are replaced by H.sup.+. The ratio of europium to phosphorus is thus 0.272 to 1.00, which corresponds to replacement of 82% of the acidic protons in the polymer (A). On irradiation with UV light at λ=366 nm, the polymer exhibits a pale orange fluorescence, whereas it fluoresces intensely pink at λ=254 nm. A quantum yield of 3.6% is determined with the aid of fluorescence spectroscopy. Excitation at λ=250.0 nm causes maximum absorption with emission maxima at λ=590.0 nm (Δv.sub.1/2=9.8 nm) and 610.5 nm (Δv.sub.1/2=9.7 nm).
EXAMPLE 28
Extraction of Terbium Chloride using polypentafluoroethyl-4-styrylphosphinic acid
[0430] ##STR00063##
[0431] Polypentafluoroethyl-4-styrylphosphinic acid, [(C.sub.2F.sub.5)(4-styryl)P(O)OH.Math.0.5H.sub.2O].sub.n (52 mg; 0.176 mmol), is added to a solution of TbCl.sub.3 (55 mg; 0.207 mmol) in H.sub.2O (1 ml) in an FEP reactor (Ø.sub.i=8 mm), and the mixture is stirred at RT. After 22 h, the white suspension with bulky precipitate (A) is centrifuged, the mother liquor is decanted and the white solid (A) is washed with H.sub.2O (2×1 ml). The combined mother liquors are evaporated at RT in vacuo (10.sup.−3 mbar), and the resultant white and solid residue (B) (62 mg) is dried at RT in vacuo (10.sup.−3 mbar) for a further 2 h. The white solid (B) fluoresced yellow-green (TbCl.sub.3) on irradiation with UV light (λ=254 nm). Analogously to the experiment with europium (Example 6), the residue here can again be assumed to be a hexaaqua complex, [Tb(H.sub.2O).sub.6]Cl.sub.3. The water content is estimated as 18 mg (1.0 mmol). Elemental analysis of the solid shows little contamination by CH.sub.3CN (1 mg; 0.02 mmol) from the starting material. No chloride was detected in the polymer (A) by X-ray fluorescence analysis. The ratio of terbium to phosphorus is 0.33 to 1.00. TbCl.sub.3 (62 mg−18 mg (H.sub.2O)−1 mg (CH.sub.3CN)=43 mg (0.162 mmol)) can be isolated as white solid (A). Tb.sup.3+ (0.045 mmol) in the polymer are replaced by H.sup.+. The ratio of terbium to phosphorus is thus 0.26 to 1.00, which corresponds to replacement of 77% of the acidic protons in the polymer (A). On irradiation with UV light at λ=254 nm, the polymer (A) likewise fluoresces yellow-green.
EXAMPLE 29
Graft Polymerisation of (C.SUB.2.F.SUB.5.)(CH.SUB.2.═CHCH.SUB.2.CH.SUB.2.)P(O)OH on a Porous Polymer Support (Hydrophilic Crosslinked Polyvinyl Ether) using [NH.SUB.4.].SUB.2.cerium[NO.SUB.3.].SUB.6 .in H.SUB.2.O at 40° C.
[0432] White and solid polymer gel (−20 g) (filtered out of H.sub.2O suspension) is initially introduced in a 500 ml 3-necked round-bottomed flask with reflux condenser, dropping funnel and precision glass stirrer, and an aqueous (C.sub.2F.sub.5)(CH.sub.2═CHCH.sub.2CH.sub.2)P(O)OH solution (18.77 g in 100 ml of water) is added. As initiator, an aqueous [NH.sub.4].sub.2cerium[NO.sub.3].sub.6 (2.41 g)/HNO.sub.3 (65%, 1.44 g) solution (20 ml) is placed in the dropping funnel. The entire apparatus is degassed in a membrane-pump vacuum (100 mbar) and flooded with N.sub.2. The reaction suspension is warmed (40° C.) and the initiator substance is subsequently added. The now-yellow suspension is stirred at 40° C. for 22 h. The mixture is subsequently filtered, and the filter cake is washed with water (2×100 ml). The pale-yellow polymer material is washed with water (3×100 ml) and an H.sub.2SO.sub.4 (concentrated, 25 g)/ascorbic acid (17.6 g) solution (500 ml)(5×100 ml). The mixture is subsequently washed neutral several times more with an NaHPO.sub.4/NaOH buffer solution (pH 7, 50 mM) and water (in total 1000 ml). The slightly beige-coloured polymer material is stored in the refrigerator at 0° C. under Millipur water. A polymer material forms in which 0.9 g of the phosphinic acid employed is bonded to 1 g of polymer.
[0433] The polymer material obtained is in addition investigated by solid-state and liquid NMR spectroscopy. The signals detected are comparable with those of but-3-en-1-ylpentafluoroethylphosphinic acid and can be assigned to the structural unit
##STR00064##
EXAMPLE 30
Polymerisation in the Presence of a Silica-Gel Support Material
[0434] Step 1: Preparation of Mercapto-Silica Gel
[0435] Object: Synthesis of LiChroprep Mercapto from LiChroprep Si 100; 15 μm-25 μm. LiChroprep Si 100 as an average pore size of 10 nm.
[0436] LiChroprep Si 100 is a traditionally prepared irregular SiO.sub.2 sorbent (silica gel) having an average pore size of 10 nm and an average particle size of 15 μm to 25 μm. LiChroprep Si is merely a trade name. Silica gels of this type are prepared in accordance with the prior art and are known to the person skilled in the art.
[0437] Equipment: 1l 3-necked flask, precision glass stirrer, reflux condenser, oil-bath heating 90° C., nitrogen feed, 50 ml dropping funnel, 1x stirrer, 2x glass suction filters 1l Por. 4
[0438] 1×2000 ml three-necked flask, 2×2l suction bottle, 1x porcelain dish
TABLE-US-00003 TABLE 1 Chemicals used: Amount Chemical Art. No. Batch Property 100.1 g LiChroprep Si F553395 S.sub.BET = 282.2 m.sup.2/g 100 (15-25 μm) 4.1086 g Sodium acetate 1.06268 A0472968 322 0.1M 43.1 g Mercapto- AB111217 1068410 180.34 g/mol 43.1 ml propylmethyl- ABCR dimethoxysilane w = 95% Dist. water — — 1.3 l Methanol 1.06009.5000 I734309416
[0439] Procedure:
[0440] 100.1 g of LiChroprep Si100 are initially introduced in a 1000 ml three-necked flask and suspended in 0.1 molar sodium acetate solution at 250 rpm.
[0441] The mercaptopropylmethyldimethoxysilane should be added dropwise over the course of 10 to 15 minutes with stirring.
[0442] The suspension is heated under reflux (90° C.) for 3 hours.
[0443] After heating for 3 hours, the suspension is slowly cooled to room temperature with stirring.
[0444] The gel is then filtered off with suction on a 1 l Por4 frit, suspended again with 1 l of deionised water and filtered off with suction. The gel is transferred into a 2 l three-necked flask, and 1 l of methanol is added. The suspension is heated at 65-69° C. for 30 minutes. After cooling to room temperature, the reaction mixture is filtered off with suction on a 1 l Por4 frit, rinsed twice with 100 ml of methanol and dried over vacuum for 1 hour. The product is left to stand overnight in the fume hood without vacuum and next day dried again for 3 hours in vacuo.
[0445] Elemental analysis: C=6.3%, S=4.0%
[0446] 2nd Step Addition of but-3-en-1-yl(pentafluoroethyl)phosphinic acid
[0447] Product batch: ScW14FE002
[0448] Equipment:
[0449] 2×250 ml three-necked flasks
[0450] condenser
[0451] precision glass stirrer and stirrer sleeve
[0452] hotplate
[0453] thermometer and oil bath
[0454] 1000 μl Eppendorf pipette equi No.: 70221348
[0455] analytical balance equ No.: 70081915
[0456] 125 ml Por.4 frit
TABLE-US-00004 TABLE 2 Chemicals: Molar Equivalence Weight/ Chemical Article number/batch amount milimol volume Mercapto- ScW14FE001 1.2699 mmol/g 4.5 μmol/m.sup.2 4.4990 g silica gel 5.77 mmol But-3-en-1-yl- 13.71 mmol 2.4 3.2562 g (pentafluoro- ethyl)phosphinic acid Glacial acetic K28057163032 9 mmol 2 mmol/g 0.540 g acid 1.00063.1000 of silica 0.515 ml V65 1.1142 mmol 20% mol 0.2836 g Methanol I734309416 90 ml 1.06009.5000
[0457] Procedure:
[0458] The mercapto-silica gel (ScW14FE001) was initially introduced in a three-necked flask with 40 ml of methanol and suspended under nitrogen. The 3-butenylpentafluoroethylphosphinic acid, the glacial acetic acid and the V65 were then added. The vessels in which the weighed amounts were located were rinsed twice with a small amount of methanol. The reaction mixture was boiled at a bath temperature of 67° C. for 6h under nitrogen. The lukewarm reaction solution was filtered off with suction via a 125 ml Por.4 frit.
[0459] The gel was transferred into another 250 ml three-necked flask, boiled with about 50 ml of methanol for 5 min with stirring and filtered off with suction. This washing step was repeated 3 times.
[0460] The gel was dried firstly in a fume hood overnight and then at 30° C. in a vacuum drying cabinet for 16 hours.
[0461] Elemental analysis:
[0462] 3. Determination of the Terbium Chloride Binding Capacity
[0463] Equipment:
[0464] 10, 25 and 100 ml volumetric flasks
[0465] Ultrospec 4000 UV spectrometer, Pharmacia Biotech, Inv. No. 59485
[0466] ultrasound bath
[0467] Sartorius BP221 F analytical balance Equ Nr:70098279
[0468] Eppendorf 5804 centrifuge, Equ No.: EM 2363
TABLE-US-00005 TABLE 3 chemicals used Molecular Article number/ weight or Chemical batch S.sub.BET Terbium chloride hexahydrate 1315353 265.29 (TbCl3*6H2O) LiChroprep Si 100, 15-25 μm F553395 Mercapto-silica gel ScW14FE001 Silica gel from step 2 ScW14FE002 Water, MilliQ
A calibration curve of the adsorption of terbium chloride hexahydrate in water at 220 nm in the range from 0.018 to 1.832 mg/ml is recorded. The line of best fit followed the line equation y=0.8502 x+0.009 where R.sup.2=0.999.
[0469] In each case 10 ml of a stock solution of 0.521 mg of TbCl.sub.3*6 H.sub.2O in water are added to about 200 mg (weighed precisely) of the respective silica gel, as indicated in Table 4, in a sealed glass vessel and left in the ultrasound bath in parallel for 10 min. In each case 5 ml of the solution are subsequently centrifuged at 5000 rpm for 5 min and the adsorption of the supernatant at 220 nm is measured.
TABLE-US-00006 TABLE 4 Results: Adsorption (220 nm) of the Sample supernatant Stock solution (0.521 mg of 0.437 TbCl.sub.3 * 6 H.sub.2O in water) Silica gel LiChroprep Si 100, 0.401 15-25 μm Silica gel from step 2 0.148
Measurement of the TbCl.sub.3 adsorption shows a decrease of 70%, which corresponds to the amount of Tb cations bound.