Polysilylated organosilane compounds

Abstract

The invention concerns a mono- or polyfunctional polysilylated organosilane compound, and the method for preparing same.

Claims

1. A compound selected from the group consisting of the following formulas: ##STR00094## ##STR00095## ##STR00096## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6, either identical or different, represent a hydrogen atom, a C.sub.1-C.sub.6-alkyl group, an aryl group, a C.sub.1-C.sub.6-alkoxy group, a C.sub.3-C.sub.8-alkylene-alkenyl group; E.sup.1, E.sup.2, E.sup.3, E.sup.4, E.sup.5 and E.sup.6, either identical or different, represent a C.sub.1-C.sub.6-alkylene group, C(O), CCH.sub.2 group, an imino-C.sub.1-C.sub.6-alkyl group, a group (C.sub.1-C.sub.6-alkyl)CN; d, e, f, g, h, i, either identical or different, represent 0, 1, 2, 3, 4, 5, 6; j, k, l, m, n, o, either identical or different, represent 0, 1, 2, 3; a represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; B represents a group CR.sup.12R.sup.13 b represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; Q represents a hydrogen atom; q represents 0 or 2; E.sup.7, and E.sup.12 either identical or different, represent a group CR.sup.14R.sup.15; R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, and R.sup.15, either identical or different, represent a hydrogen atom, a C.sub.1-C.sub.6-alkyl group, a C.sub.1-C.sub.6-alkoxy group, a C.sub.3-C.sub.8-alkylene-alkenyl group, an aryl group, or an aryloxy group; J represents a terminal atom or group, an atom or a divalent, trivalent, tetravalent, pentavalent or hexavalent, mono- or polyfunctional group; p and w, either identical or different, represent 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; J.sup.1 represents an atom or a divalent, trivalent, tetravalent, pentavalent or hexavalent, mono- or poly-functional group; y represents 2, 3, 4, 5, 6; J.sup.2 represents a divalent, mono- or poly-functional group; J.sup.3 represents a trivalent, mono- or poly-functional group; as well as an enantiomer, an isomer or a diastereoisomer of this compound.

2. The compound according to claim 1, wherein A and B represents a group (CH.sub.2); or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent independently a Me or Et group; or a represents 1, 2 or 3; or b represents 1, 2 or 3; or d, e, f, g, h and i, either identical or different, represent 0 or 1; or j, k, l, m, n and o represent 0.

3. The compound according to claim 1, wherein A and B represent a group (CH.sub.2); Q represents a hydrogen atom; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent independently an Me or Et group; a represents 1, 2 or 3; b represents 1, 2 or 3; d, e, f, g, h and i, either identical or different, represent 0 or 1; j, k, 1, m, n and o represent 0.

4. The compound according to claim 1 wherein: A and B represents a group (CH.sub.2); a represents 1, 2 or 3; b represents 1, 2 or 3.

5. The compound according to claim 1, wherein J, J.sup.1, J.sup.2, and J.sup.3 represent independently a mono- or poly-functional group comprising at least one functional group selected from the group consisting of a coloring group, a catalyst group, a group allowing molecular recognition, a biologically active group, a redox group, a hydrophilic group, a hydrophobic group, a decontaminating complexing group, a catalyst complexing group, and a cross-linking group.

6. The compound according to claim 1, wherein the functional group is selected from: a colouring group selected from an azoic, triphenylmethane, phthalein, a quinonic, an indigoid, an azinic, a porphyrin, a phthalocyanin, boron-dipyromethene, naphthalimide, polyaromatic, pyrene, acridine, and derivatives thereof, a colouring agent comprising a conjugate system, a fluorescent colouring agent or a phosphorescent colouring agent; a catalyst group selected from a proline, a prolinamide, a diaryl-prolinol, 1, 1-bis-2-naphthol, trans-1,2-diaminocyclohexane, tartaric acid, 1,2-diphenylethylenediamine, bisoxazoline, phosphine-oxazoline, pyridine-bisoxazoline, triarylphosphine, diphosphine, an imidazolium salt, a N-heterocyclic metal-carbene complex, a bipyridine, a pyridine, a phenanthroline, cyclopentadiene and derivatives thereof; a group allowing molecular recognition selected from a nitrogen-containing base, a melamine and derivatives thereof; a redox group selected from a metallocene, 1,4-(4-aminophenyl)-butadiene, a fullerene, a carbon nanotube and derivatives thereof; a hydrophobic group selected from a C.sub.1-C.sub.30 alkyl group, non-substituted or substituted with at least one fluorine atom, an aryl group; a decontaminating complexing group selected from an amine, an alcohol, a pyridine, a bipyridine, a triarylphosphine, a malonamide, a diacid, a diketone and derivatives thereof; a catalyst complexing group selected from a proline, a diarylprolinol and derivatives thereof; a cross-linking group selected from butadiene, butadiyn, an acrylate, a methacrylate, vinyl, styryl and derivatives thereof; a structuring group selected from a pyrrole, thiophene, alkylene or phenylene.

7. The compound according to claim 1 wherein J represents a mono- or poly-functional group comprising at least one functional group selected from: a colouring group selected from boron-dipyromethene, a naphthalimide, a porphyrin, a phthalocyanin, an azoic, an indigoid, a phthalein, a quinonic and derivatives thereof; a decontaminating complexing group selected from an amine, an alcohol, a pyridine, a triarylphosphine, a malonamide, a diacid, a diketone and derivatives thereof; a group allowing molecular recognition selected from a nitrogen-containing base, a melamine and derivatives thereof; a catalyst complexing group selected from a proline, a diarylprolinol and derivatives thereof; a redox group selected from a metallocene; a hydrophobic group selected from a C.sub.1-C.sub.30 alkyl group, non-substituted or substituted with at least one fluorine atom; a structuring group selected from a pyrrole or a thiophene.

8. The compound according to claim 1 wherein J.sup.2 represents a mono- or poly-functional group comprising at least one functional group selected from: a colouring group selected from boron-dipyromethene, a porphyrin, a phthalocyanin, an azoic, an indigoid, a phthaleine, a quinonic, triphenylmethane, a colouring agent comprising at least a conjugate system, a pyrene and derivatives thereof; a decontaminating complexing group selected from a pyridine, a bipyridine, a triarylphosphine, a malonamide, a diketone and derivatives thereof; a group allowing molecular recognition selected from a melamine and derivatives thereof; a catalyst group selected from a binol, a derivative of 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP), a derivative of 2,2-diamino-1,1-binaphthyl (BINAM), trans-1,2-diaminocyclohexane, 1,2-diphenylethylene-1,2-diamine, tartaric acid and derivatives thereof; a redox group selected from 1,4-(4-aminophenyl)-butadiene, a metallocene and derivatives thereof; a hydrophobic group selected from a C.sub.1-C.sub.30 alkyl group, non-substituted or substituted with at least one fluorine atom, an aryl group; a structuring group selected from a thiophene, an alkylene.

9. The compound according to claim 1 wherein J.sup.3 represents a mono- or poly-functional group comprising at least one functional group selected from: a decontaminating complexing group selected from a triarylphosphine and derivatives thereof, a group allowing molecular recognition selected from a melamine and derivatives thereof, a structuring group such as a phenylene.

Description

EXAMPLE 1: PREPARATION OF POLYSILYLATED ORGANOSILANE COMPOUNDS ACCORDING TO THE INVENTION

(1) All the exemplified polysilylated organosilane compounds were obtained by the reaction between: a compound 1 of formula

(2) ##STR00052## and an organic nitride.

(3) In a micro-wave reactor, were introduced the compound 1 (2.0 mmol), the organic nitride (2.0 mmol of nitride function), the catalyst [CuBr(PPh.sub.3).sub.3], in a 1:1 mixture THF/Et.sub.3N (1 ml).

(4) The mixture was irradiated at 100 C. for the indicated time, and then the volatile compounds were evaporated. After extraction with pentane (32 ml) and then concentration, the compounds 2 to 11 were obtained.

(5) Table I shows the structures of the organic nitrides used and the structures of the corresponding polysilylated organosilane compounds 2 to 11.

(6) TABLE-US-00001 TABLE I Organic nitrides Polysilylated organosilane compounds 2 3 4 0 5 6 7 8 9 0 10 11

(7) The characteristics of each reaction ending up with the compounds 2 to 11, as well as the NMR characterisation of each obtained product are described.

(8) Compound 2

(9) Cat 0.5%; time: 10 min; yield: 97%.

(10) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.41 (s, 1H), 4.59-4.40 (m, 2H), 4.10-3.90 (m, 4H), 3.71 (t, J=7.0 Hz, 12H), 3.67 (s, 2H), 2.44-2.9 (m, 6H), 1.49 (m, 4H), 1.24 (t, J=7.1 Hz, 6H), 1.12 (t, J=7.0 Hz, 18H), 0.57-0.34 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.9, 122.4, 62.0, 58.2, 56.6, 48.8, 44.3, 27.9, 26.5, 20.4, 18.2, 16.3, 7.8.

(11) HRMS (ESI.sup.+):

(12) m/z calculated for C.sub.27H.sub.60N.sub.4O.sub.9Si.sub.2P, 671.3637

(13) m/z determined: 671.3635.

(14) Compound 3

(15) Cat: 0.5%; time: 5 min; yield: 96%.

(16) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.19-7.94 (m, 8H), 7.83 (d, J=7.8 Hz, 1H), 7.19 (s, 1H), 6.14 (s, 2H), 3.71 (q, J=7.0 Hz, 12H), 3.66 (s, 2H), 2.42-2.21 (m, 4H), 1.56-1.39 (m, 4H), 1.13 (t, J=7.0 Hz, 18H), 0.55-0.37 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =146.1, 132.0, 131.1, 130.5, 129.2, 128, 128.2, 127.4, 127.2, 127.1, 126.3, 125.8, 125.7, 125.0, 124.9, 124.4, 122.2, 121.9, 58.2, 56.6, 52.3, 48.8, 20.3, 18.2, 7.8.

(17) HRMS (ESI.sup.+):

(18) m/z calculated for C.sub.38H.sub.57N.sub.4O.sub.6Si: 721.3817;

(19) m/z determined: 721.3830.

(20) Compound 4

(21) Cat: 0.5%; time: 10 min; yield: 91%.

(22) .sup.1H NMR (250 MHz, CDCl.sub.3) =7.37 (bs, 2H), 7.23 (s, 4H), 5.49 (s, 4H), 3.81 (q, J=7.0 Hz, 24H), 3.77 (s, 4H), 2.47-2.32 (m, 8H), 1.69-1.40 (m, 8H), 1.19 (t, J=7.0 Hz, 36H), 0.61-0.44 (m, 8H). .sup.13C NMR (101 MHz, CDCl.sub.3) =146.2, 135.4, 128.5, 122.2, 58.2, 56.6, 53.3, 48.8, 20.3, 18.2, 7.8.

(23) HRMS (ESI.sup.+)

(24) m/z calculated for C.sub.50H.sub.99N.sub.8O.sub.12Si.sub.4: 1115.6460;

(25) m/z determined: 1115.6447.

(26) Compound 5

(27) Cat: 0.5%; time: 5 min; yield: 87%.

(28) .sup.1H NMR (250 MHz, CDCl.sub.3) =7.38 (s, 2H), 4.26 (t, J=7.3 Hz, 4H), 3.75 (q, J=7.0 Hz, 24H), 3.71 (s, 4H), 2.45-2.30 (m, 8H), 1.92-1.75 (m, 4H), 1.63-1.43 (m, 8H), 1.30-1.20 (bs, 12H), 1.36 (t, J=7.0 Hz, 36H), 0.58-0.45 (m, 8H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.8, 122.0, 58.3, 56.7, 50.1, 48.9, 30.3, 29.2, 28.9, 26.4, 20.4, 18.3, 7.9.

(29) HRMS (ESI.sup.+):

(30) m/z calculated for C.sub.52H.sub.111N.sub.8O.sub.12Si.sub.4: 1151.7399;

(31) m/z determined: 1151.7421.

(32) Compound 6

(33) Cat: 1%; time: 15 min; yield: 90%.

(34) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.17 (s, 3H), 5.67 (s, 2H), 5.64 (s, 4H), 3.82 (q, J=7.0 Hz, 36H), 3.74 (s, 6H), 2.61-2.31 (m, 21H), 1.67-1.46 (m, 12H), 1.23 (t, J=7.0 Hz, 54H), 0.66-0.41 (m, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) =146.0, 139.6, 130.7, 121.7, 58.2, 56.6, 48.9, 20.2, 18.2, 16.5, 7.9, 0.9.

(35) Compound 7

(36) Cat: 0.5%; time: 5 min; yield: 95%.

(37) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.38-7.31 (m, 5H), 7.25-7.20 (m, 1H), 5.50 (s, 2H), 3.78 (q, J=7.0 Hz, 12H), 3.74 (s, 2H), 2.44-2.34 (m, 4H), 1.62-1.46 (m, 4H), 1.19 (t, J=7.0 Hz, 18H), 0.59-0.48 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =146.5, 135.0, 129.1, 128.7, 128.0, 122.3, 58.3, 56.8, 54.1, 49.0, 20.5, 18.4, 8.0.

(38) HRMS (ESI.sup.+):

(39) m/z calculated for C.sub.28H.sub.53N.sub.4O.sub.6Si.sub.2: 597.3504;

(40) m/z determined: 597.3514.

(41) Compound 8

(42) Cat: 0.5%; time: 24 h at room temperature; yield: 94%.

(43) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.37 (s, 1H), 4.27 (t, J=7.3 Hz, 2H), 3.76 (q, J=7.0 Hz, 12H), 3.72 (s, 2H), 2.42-2.34 (m, 4H), 1.88-1.77 (m, 3H), 1.58-1.48 (m, 4H), 1.26 (bs, 8H), 1.17 (t, J=7.0 Hz, 18H), 0.57-0.49 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.9, 122.0, 58.3, 56.8, 50.2, 49.0, 31.2, 30.3, 26.2, 22.4, 20.5, 18.3, 13.9, 8.0.

(44) HRMS (ESI.sup.+):

(45) m/z calculated for C.sub.27H.sub.59N.sub.4O.sub.6Si.sub.2: 591.3973;

(46) m/z determined: 591.3969.

(47) Compound 9

(48) Cat: 1%; time: 15 min; yield: 95%.

(49) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.41 (s, 1H), 4.30 (t, J=7.3 Hz, 2H), 3.80 (q, J=7.0 Hz, 12H), 3.76 (s, 2H), 3.62 (t, J=6.6 Hz, 2H), 2.63-2.55 (m, 1H), 2.42 (t, J=8.0 Hz, 4H), 1.92-1.82 (m, 2H), 1.65-1.49 (m, 4H), 1.37-1.23 (b, 14H), 1.21 (t, J=7.0 Hz, 18H), 1.07 (t, J=7.2 Hz, 2H), 0.61-0.53 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.9, 122.1, 63.0, 58.4, 56.8, 50.3, 49.1, 32.9, 30.4, 29.5, 29.4 (3C), 29.0, 26.5, 25.8, 20.5, 18.4, 8.0.

(50) HRMS (ESI.sup.+):

(51) m/z calculated for C.sub.32H.sub.69N.sub.4O.sub.7Si.sub.2: 677.4705;

(52) m/z determined: 677.4698.

(53) Compound 10

(54) Cat: 1%; time: 20 min; yield: 94%.

(55) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.41 (s, 1H), 4.30 (t, J=7.2 Hz, 2H), 3.78 (t, J=7.0 Hz, 12H), 3.77 (t, J=7.0 Hz, 6H), 3.75 (s, 2H), 2.41 (t, J=780 Hz, 4H), 2.03-1.94 (m, 2H), 1.63-1.48 (m, 4H), 1.19 (t, J=7.0 Hz, 9H), 1.18 (t, J=7.0 Hz, 18H), 0.62-0.51 (m, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.6, 122.3, 58.6, 58.4, 56.8, 52.5, 49.0, 24.4, 20.5, 18.4 (2C), 8.0, 7.6.

(56) HRMS (ESI.sup.+):

(57) m/z calculated for C.sub.30H.sub.67N.sub.4O.sub.9Si.sub.3: 711.4216;

(58) m/z determined: 711.4212.

(59) Compound 11

(60) Cat: 1%; time: 10 min; yield: 91%.

(61) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.33 (s, 1H), 7.91 (s, 1H), 7.52 (s, 1H), 6.14 (s, 2H). 4.32 (t, J=6.4 Hz, 2H), 4.23 (t, J=6.5 Hz, 2H), 3.77 (q, J=7.0 Hz, 12H), 3.73 (s, 2H), 2.52-2.46 (m, 2H), 2.44-2.36 (m, 4H), 1.60-1.49 (m, 4H), 1.17 (t, J=7.0 Hz, 18H), 0.58-0.50 (m, 4H), .sup.13C NMR (101 MHz, CDCl.sub.3) =155.8, 153.1, 146.4, 132.2, 132.1, 128.6, 122.7, 58.3, 56.9, 49.0, 46.8, 40.9, 30.5, 20.6, 18.4, 8.0.

(62) HRMS (ESI.sup.+):

(63) m/z calculated for C.sub.29H.sub.56N.sub.90O.sub.6Si.sub.2: 682.3892;

(64) m/z determined: 682.3894.

EXAMPLE 2: PREPARATION OF POLYSILYLATED ORGANOSILANE COMPOUNDS ACCORDING TO THE INVENTION

(65) All the exemplified polysilylated organosilane compounds were obtained by the reaction between: a compound of formula 12

(66) ##STR00073## and an organic nitride.

(67) In a microwave reactor were introduced the compound 12 (2.0 mmol), the organic nitride (4.0 mmol of nitride function), the catalyst [CuBr(PPh.sub.3).sub.3], in a 1:1 mixture THF/Et.sub.3N (1 ml).

(68) The mixture was irradiated at 100 C. for the indicated time, and then the volatile compounds were evaporated. After extraction with pentane (32 ml) and then concentration, the products 13 and 14 were obtained.

(69) Table II shows the structures of the organic nitrides used and the structures of the corresponding polysilylated organosilane compounds 13 and 14.

(70) TABLE-US-00002 TABLE II Organic nitrides Polysilylated organosilane compounds 13 14 22

(71) The characteristics of each reaction ending up with the compound 13, 14 and 22 as well as the NMR characterisation of each obtained product, are described.

(72) Compound 13

(73) Cat: 0.5%; time: 10 min; yield: 90%.

(74) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.44-7.28 (m, 8H), 7.26-7.21 (m, 4H), 5.49 (s, 4H), 3.77 (q, J=7.0 Hz, 12H), 3.70 (s, 4H), 2.52 (s, 4H), 2.41-2.35 (m, 4H), 1.59-1.47 (m, 4H), 1.19 (t, J=7.0 Hz, 18H), 0.55-0.48 (m, 4H). .sup.13C NMR (63 MHz, CDCl.sub.3) =145.8, 134.9, 129.0, 128.5, 127.9, 122.5, 58.2, 57.4, 53.9, 51.7, 49.0, 20.4, 18.3, 7.8.

(75) HRMS (ESI.sup.+):

(76) m/z calculated for C.sub.40H.sub.67N.sub.8O.sub.6Si.sub.2: 811.4722;

(77) m/z determined: 811.4726

(78) Compound 14

(79) Cat 0.5%, time: 20 min, yield: 94%.

(80) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.18-7.80 (m, 18H), 7.89 (s, 2H), 6.10 (s, 4H), 3.69 (q, J=7.0 Hz, 12H), 3.49 (s, 4H), 2.36 (s, 4H), 2.22 (t, J=4 Hz, 4H), 1.45-1.42 (m, 4H), 1.12 (t, J=7.0 Hz, 18H), 0.42-0.34 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =145.8, 131.9, 131.1, 130.5, 129.1, 128.8, 128.1, 127.4, 127.3, 127.2, 126.3, 125.8, 125.7, 124.9 (2C), 124.4, 122.6, 122.0, 58.3, 57.4, 53.1, 52.2, 48.9, 20.2, 18.3, 7.8.

(81) HRMS (ESI.sup.+):

(82) m/z calculated for C.sub.60H.sub.75N.sub.8O.sub.6Si.sub.2: 1059.5348;

(83) m/z determined: 1059.5354.

(84) Compound 22

(85) Cat 1%, time: 25 min, yield 75%:

(86) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.63 (s, 2H), 5.15 (s, 4H), 4.24 (q, J=7.3 Hz, 4H), 3.80 (q, J=7.1 Hz, 12H), 2.59 (br, 4H), 2.45 (m, 4H), 2.12 (br, 4H), 1.59 (m, 4H), 1.29 (t, J=7.4 Hz, 6H), 1.22 (t; J=7.1 Hz, 18H), 0.56 (m, 4H). .sup.13C NMR (, ppm): 166.6; 124.3; 62.4; 58.5; 58.3; 57.6; 51.7; 50.9; 49.1; 20.6; 18.5; 14.2; 8.0.

EXAMPLE 3: PREPARATION OF A POLYSILYLATED ORGANOSILANE COMPOUND ACCORDING TO THE INVENTION

(87) In a micro-wave reactor were introduced: a compound of formula 15 (2.0 mmol)

(88) ##STR00080## an organic alkyne (2.0 mmol of alkyne function) of formula

(89) ##STR00081## a catalyst [CuBr(PPh.sub.3).sub.3],
in a 1:1 mixture THF/Et.sub.3N (1 ml).

(90) The mixture was irradiated at 100 C. for the indicated time, and then the volatile compounds were evaporated. After extraction with pentane (32 ml) and then concentration, the product 16 was obtained.

(91) ##STR00082##

(92) Cat 0.5%, time: 10 min, yield: 91%; solvent: DMF/Et.sub.3N au lieu de THF/Et.sub.3N.

(93) .sup.1H NMR (400 MHz, CDCl.sub.3) =8.34 (s, 1H), 7.98 (s, 1H), 7.63 (s, 1H), 6.09 (s, 2H), 5.46 (s, 2H), 4.33 (t, J=7.3 Hz, 2H), 3.77 (q, J=7.0 Hz, 12H), 2.39 (t, J=8 Hz, 2H), 2.35 (t, J=8 Hz, 4H), 2.01-1.92 (m, 2H), 1.51-1.40 (m, 4H), 1.18 (t, J=7.0 Hz, 18H), 0.56-0.49 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) =155.7, 153.1, 149.8, 142.2, 140.5, 123.1, 119.6, 58.4, 56.8, 50.7, 48.7, 36.7, 28.3, 20.2, 18.4, 8.0.

(94) HRMS (ESI.sup.+):

(95) m/z calculated for C.sub.29H.sub.56N.sub.90O.sub.6Si.sub.2: 682.3895;

(96) m/z determined: 682.3895

EXAMPLE 4: PREPARATION OF A POLYSILYLATED ORGANOSILANE COMPOUND ACCORDING TO THE INVENTION

(97) In a micro-wave reactor, were introduced: a compound of formula 15 (2.0 mmol),

(98) ##STR00083## an organic alkyne (2.0 mmol of alkyne function) of formula

(99) ##STR00084## a catalyst [CuBr(PPh.sub.3).sub.3],
in a 1:1 mixture THF/Et.sub.3N (1 ml).

(100) The mixture was irradiated at 100 C. for the indicated time, and then the volatile compounds were evaporated. After extraction with pentane (32 ml) and then concentration, the product 17 was obtained.

(101) ##STR00085##

(102) Cat 0.5%, time: 10 min, yield: 96%.

(103) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.35 (s, 2H), 5.09 (q, J=8.8 Hz, 2H), 4.30 (s, 2H), 4.11 (t, J=7.8 Hz, 4H), 3.52 (q, J=7.2 Hz, 24H), 2.41-2.25 (bs, 2H), 2.21-2.05 (m, 12H), 1.81-1.68 (m, 4H), 1.28-1.55 (m, 8H), 0.93 (t, J=7.2 Hz, 36H), 0.82-0.74 (m, 2H), 0.34-0.24 (m, 8H). .sup.13C NMR (101 MHz, CDCl.sub.3) =171.4, 142.0, 124.0, 67.3, 72.4, 58.5, 56.9, 50.7, 50.3, 28.4, 20.3, 18.5, 8.1.

(104) HRMS (ESI.sup.+):

(105) m/z calculated for C.sub.52H.sub.107N.sub.8O.sub.18Si.sub.4: 1243.6780;

(106) m/z determined: 1243.6793

EXAMPLE 5: PREPARATION OF AN ORGANOSILICON MATERIAL WITH A PYRENE FUNCTION

(107) A material of formula 18 was prepared with two different methods:

(108) ##STR00086##
By Acid Catalysis

(109) A mixture of compound 3 (5.7 mmol), of distilled water (122 ml, 6.8 mol) and of hydrochloric acid (12 M, 0.2 ml, 2.4 mmol), was vigorously stirred for one hour at 80 C. in a sealed tube, and then kept at rest at 80 C. for 48 hours.

(110) The composition of the mixture was: compound 3/H.sub.2O/HCl=1:1200:0.4.

(111) After cooling, the precipitate was spin-dried, successively washed with water, acetone and then ether, and dried under reduced pressure for 3 hours.

(112) The thereby obtained product is characterized in the following way:

(113) IR (wavenumbers in cm.sup.1): 706; 842; 1023; 1186; 1456; 1589; 2880; 2931; 3047.

(114) .sup.13C NMR CPMAS (, ppm): 146; 126; 62; 58; 22; 12.

(115) .sup.29Si NMR CPMAS (, ppm): 51 (T.sup.1): 59 (T.sup.2); 67 (T.sup.3); Condensation rate: 90%

(116) Elementary analysis: H, 4.5%; C, 52.5%; N, 8.9%.

(117) By Nucleophilic Catalysis

(118) A solution of tetrabutylammonium fluoride (1 M in THF, 0.10 ml, 0.10 mmol) and of distilled water (1.2 ml, 66 mmol) were added to a solution of compound 3 (5.6 mmol) in dry ethanol (20 ml).

(119) The composition of the mixture was: compound 3/water/TBAF=1:12:0.02.

(120) The formation of a gel was observed after 20 minutes. After 48 hours under static conditions, the gel was crushed on a frit, and then successively washed with water, acetone and then ether, and finally dried under reduced pressure for 3 hours.

(121) The thereby obtained product is characterized in the following way:

(122) IR (wavenumbers in cm.sup.1): 706; 842; 1045; 1086; 1455; 1589; 2880; 2929; 2972; 3329.

(123) .sup.13C NMR CPMAS (, ppm): 146; 126; 62; 58; 52; 22; 19; 12.

(124) .sup.29Si NMR CPMAS (, ppm): 51 (T.sup.1): 59 (T.sup.2); 67 (T.sup.3); Condensation rate: 81%.

(125) Elementary analysis: H, 6.37%; C, 59.4%; N, 9.2%.

EXAMPLE 6: PREPARATION OF AN ORGANOSILICON MATERIAL WITH A PROLINE FUNCTION

(126) A material of formula 19 was obtained with the following method:

(127) ##STR00087##

(128) A solution of tetrabutylammonium fluoride (1 M in THF, 0.10 ml, 0.10 mmol) and of distilled water (1.2 ml, 66 mmol) were added to a solution of compound 20 (5.6 mmol) in dry ethanol (20 ml).

(129) ##STR00088##

(130) The composition of the mixture was: compound 20/water/TBAF=1:12:0.02.

(131) The formation of a gel was observed after 20 minutes. After 48 hours under static conditions, the gel was crushed on a frit, and then successively washed with water, acetone and then ether, and finally dried under reduced pressure for 3 hours.

(132) The product thus obtained is characterized in the following way:

(133) IR (wavenumbers in cm.sup.1): 718; 919; 1019; 1118; 1199; 1370; 1628; 1673; 1733; 2892; 2936.

(134) .sup.13C NMR CPMAS (, ppm): 173; 169; 138: 116; 84; 58; 42; 27; 19; 11

(135) .sup.29Si NMR CPMAS (, ppm): 51 (T.sup.1): 59 (T.sup.2); 67 (T.sup.3); Condensation rate: 84%.

(136) Elementary analysis: H, 5.2%; C, 32.3%; N, 10.9%.

EXAMPLE 7: PREPARATION OF AN ORGANOSILICON MATERIAL WITH PYRENE FUNCTIONS

(137) A material of formula 21 was obtained with the following method:

(138) ##STR00089##

(139) A mixture of compound (14) (1.0 mmol), of distilled water (20 ml, 1.2 mol) and of hydrochloric acid (1 M, 0.4 ml, 0.4 mmol) was vigorously stirred for 1 h at 80 C, and then left at rest at this temperature for 48 h. The precipitate was spin-dried, and successively washed with water, acetone and diethyl ether, and then dried in vacuo.

(140) The thereby obtained product was characterized in the following way:

(141) IR (wavenumber in cm.sup.1): 705; 758; 926; 1045; 1092; 1185; 1320; 1436; 1460; 1590; 1605; 2819; 2933; 3040; 3144.

(142) .sup.13C NMR CP-MAS (, ppm): 146; 126; 58; 52; 21; 12.

(143) .sup.29Si NMR CP-MAS (, ppm): 60 (T.sup.2); 68 (T.sup.3).

(144) Condensation rate: 82%.

EXAMPLE 8: PREPARATION OF AN ORGANOSILICON MATERIAL WITH ETHYL ACETATE FUNCTIONS

(145) A material of formula (23) was prepared with two different methods:

(146) ##STR00090##

(147) 1by Acid Catalysis

(148) A mixture of compound (22) (4.5 mmol), of distilled water (20 mL, 1.1 mol) and of hydrochloric acid (1 M, 2.3 mL, 2.3 mmol) was vigorously stirred for 20 h at room temperature.

(149) The composition of the mixture was 22/H.sub.2O/HCl=1:2500:5.

(150) The solvent was evaporated for obtaining the material (23). The powder was washed with methanol and dried under reduced pressure at 40 C. for 6 hours.

(151) The thereby obtained product was characterized in the following way:

(152) IR (wavenumber in cm.sup.1): 095, 1018, 1055, 1091, 1215, 1344, 1376, 1467, 1736, 2949, 3140.

(153) 2by Acid Catalysis in the Presence of a Surfactant

(154) The compound (22) (0.42 mmol) was added to a mixture of SHS (sodium hexadecyl sulphate containing 40% by weight of sodium steararyl sulphate based on the total weight of the surfactant, 130 mg, 0.38 mmol), distilled water (20 ml, 1.1 mol) and HCl (1 M, 4 ml, 4 mmol) heated to 60 C.

(155) The composition of the mixture was 22/SHS/HCl/H.sub.2O=1:0.9:9.5:3100

(156) A white precipitate appears one minute later, the mixture is left with stirring for 20 hours at 50 C. and then filtered on a buchner. The extraction was accomplished by stirring the powder in basic ethanol (5 mL of NH.sub.4OH 25% in 100 ml of ethanol) at 45 C. for 48 hours.

(157) The thereby obtained product was characterized in the following way:

(158) IR (wavenumber in cm.sup.1): 919, 1055, 1099, 1378, 1468; 1744, 2933, 3148.

EXAMPLE 9: PREPARATION OF A POLYSILYLATED ORGANOSILANE COMPOUND ACCORDING TO THE INVENTION

(159) In a micro-wave reactor were introduced: a compound of formula 15 (2.0 mmol),

(160) ##STR00091## an organic alkyne (2.0 mmol of alkyne function) of formula

(161) ##STR00092## a catalyst [CuBr(PPh.sub.3).sub.3],
in a 1:1 mixture THF/Et.sub.3N (1 ml).

(162) The mixture was irradiated at 100 C. for the indicated time, and then the volatile compounds were evaporated. After extraction with pentane (32 ml) and then concentration, the product 24 was obtained.

(163) ##STR00093##

(164) Cat 0.5%, time: 5 min, yield: 91%.

(165) .sup.1H NMR (400 MHz, CDCl.sub.3) =7.55 (s, 2H), 4.67 (s, 4H), 4.38 (t, J=7.2 Hz, 4H), 3.81 (q, J=7.1 Hz, 24H), 3.69-3.60 (m, 16H), 2.45 (t, J=6.8 Hz, 4H), 2.40 (t, J=6.8 Hz, 8H), 2.02 (m, 4H), 1.50 (m, 8H), 1.22 (t, J=7.1 Hz, 36H), 0.57 (m, 8H).

(166) .sup.13C NMR (101 MHz, CDCl.sub.3) =145.0, 122.7, 70.65 (2C), 70.60, 69.7, 64.7, 58.4, 56.9, 50.9, 48.6, 28.5, 20.3, 18.4, 8.1.

(167) HRMS (ESI.sup.+)

(168) m/z calculated for C.sub.56H.sub.118N.sub.8O.sub.17Si.sub.4, 1287.7770

(169) m/z determined: 1287.7776