WO2024121062A1 - Reduction of triphenylphosphine oxide - Google Patents

Reduction of triphenylphosphine oxide Download PDF

Info

Publication number
WO2024121062A1
WO2024121062A1 PCT/EP2023/084140 EP2023084140W WO2024121062A1 WO 2024121062 A1 WO2024121062 A1 WO 2024121062A1 EP 2023084140 W EP2023084140 W EP 2023084140W WO 2024121062 A1 WO2024121062 A1 WO 2024121062A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
process according
alkyl
value
silane
Prior art date
Application number
PCT/EP2023/084140
Other languages
French (fr)
Inventor
Fabrice Aquino
Werner Bonrath
Marius-Sven GOERG
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Publication of WO2024121062A1 publication Critical patent/WO2024121062A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)

Definitions

  • the present invention relates to an improved process for preparing triphenylphosphine (TPP) by reacting triphenylphosphine oxide (TPPO) with a catalyst in a specific solvent (or mixture of solvents).
  • TPP triphenylphosphine
  • TPP which is the compound of formula (I) is used on the industrial scale in the Wittig Ylide synthesis to prepare olefinic compounds such as vitamin A or carotenoids as well as in the Mitsunobu reactions.
  • TPP is used in stoichiometric amounts and is oxidized during these reactions to TPPO, which is the compound of formula (II)
  • TPPO-problem One common way to deal with the “TPPO-problem” is to burn the TPPO, so that it can be wasted in a secure way.
  • TPP dichloride Another option is the reduction of TPPO via TPP dichloride to TPP, so that TPP can then be re-used again.
  • Such recycling processes are known from the prior art, e.g. from EP 638 580 A1 , from Heteroatom Chemistry 26(3), 2015, p.199 - 205. Most of these recycling processes are carried out in the presence of at least one siloxane and/or at least one silane.
  • At least one catalyst which comprises as metal atom, is used as well.
  • the reduction of TPPO in the state of the art, is carried out in at least one inert solvent.
  • the solvents used for the reduction of TPPO are usually alkenes or aromatic solvents.
  • Green solvents are environmentally friendly solvents, or biosolvents, which are derived from the processing of agricultural crops, while otherwise most of the commonly used solvents (such as alkanes or aromatic solvents) are petrochemical solvents. Green solvents are vastly more eco-friendly, less toxic, less hazardous than traditional volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • the present invention relates to the process (P) for producing triphenylphosphine (compound of formula (I)) wherein triphenylphosphine oxide (the compound of formula (II)) is reacted with at least one siloxane and/or at least one silane, in the presence of at least one metal containing catalyst, and in the presence of at least one solvent of formula (III)
  • R 1 ’ is Ci-C4-alkyl
  • R 2 ’ is a C5- or a Cs-cycloalkyl, or
  • R 1 ’ and R 2 ’ form (together with the O) a 5 or 6 membered ring, which can be substituted.
  • R 1 ’ and R 2 ’ form (together with the O) a 5 or 6 membered ring, it is preferred that said ring is not substituted.
  • the process according to the present invention is carried out in the presence of at least one siloxane and/or silane.
  • siloxanes are those of formula (IV) wherein
  • R1, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a Ci-C4-alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H.
  • Preferred siloxanes are those of formula (IV), wherein
  • siloxanes are those of the formulae (IV’) and (IV”)
  • m is a value from 2 - 20’000, more preferably m is a value from 2 - 12’000, most preferably m is a value from 2 - 10’000).
  • siloxane is the siloxane of the formula (IV”).
  • Particularly suitable silanes are those compounds of formula (Va) or (Vb) or (Vc). wherein o is a value from 3 to 10; and Rg, R and Rn are independently from each other H or a Ci-Ce-alkyl or a OCi-Ce-alkyl or a phenyl group, with the proviso that at least one of the substituents Rg, R and Rn is different from H.
  • silanes of formula (Vc) are silanes of the formula (Vc’) or (Vc”) or (Vc’”) or (Vc””), preferably (Vc’) or (Vc”).
  • silanes of formula (Vb) and (Vc’) and (Vc”) are the most preferred silanes.
  • the present invention also relates to a process (P1), which is process (P), wherein the at least one siloxane is chosen from the group having the formula (IV) wherein
  • Ri, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a Ci-C4-alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H.
  • the present invention also relates to a process (PT), which is process (P1), wherein the at least one siloxane is chosen from the group having the formula (IV), Wherein R1, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a C1-C2- alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H.
  • the present invention also relates to a process (P1”), which is process (P1), wherein the at least one siloxane is chosen from the group consisting of
  • TMDS TMDS
  • PMHS TMDS and (PMHS) wherein m is a value between 10 and 100’000 (preferably m is a value from 100 - 20’000, more preferably m is a value from 1000 - 12’000, most preferably m is a value from 1000 - 10’000).
  • the present invention also relates to a process (P2), which is process (P1), (PT) or (P1 ”), wherein the at least one silane is chosen from the group having the formula (Va) and (Vb) and (Vc) wherein o is a value from 3 to 10; and Rg, R and Rn are independently from each other H or a Ci-Ce-alkyl or a OCi-Ce-alkyl or a phenyl group, with the proviso that at least one of the substituents Rg, R and Rn is different from H.
  • the present invention also relates to a process (P2’), which is process (P1), (PT) or (P1 ”), wherein the at least one silane is
  • the at least one siloxane and/or the at least one silane is usually and preferably used in an amount of 1 - 10 mol-%, preferably 2 - 8 mol-%, in regard to the compound of formula (II).
  • the present invention also relates to a process (P3), which is process (P1), (PT), (P1 ”), (P2) or (P2’), wherein the at least one siloxane and/or the at least one silane is used in an amount of 1 - 10 mol-%, in regard to the compound of formula (II).
  • the present invention also relates to a process (P3’), which is process (P1), (PT), (P1 ”), (P2) or (P2’), wherein the at least one siloxane and/or the at least one silane is used in an amount of 2 - 8 mol-%, in regard to the compound of formula (II).
  • the process according to the present invention is carried out in the presence of at least one catalyst, which comprises at least one metal atom.
  • catalysts are known from the prior art.
  • Suitable catalysts comprise at least one metal atom, wherein the metal is chosen from the group consisting of Ti, Cu, Ni and In.
  • Suitable catalysts are those of formula (VI)
  • R 3 ’, R 4 ’, R 5 ’ and R 6 ’ are independently from each other OR 7 ’, wherein R 7 ’ is a linear or branched Ci - Ce alkyl group, preferably ethyl, iso-propyl, n-propyl, iso-butyl or n-butyl; or
  • the present invention also relates to a process (P4), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3) or (P3’), wherein the at least one catalyst is chosen from the group consisting of compounds of formula (VI)
  • R 3 ’, R 4 ’, R 5 ’ and R 6 ’ are independently from each other OR 7 ’, wherein R 7 ’ is a linear or branched Ci - Ce alkyl group, preferably R 7 is ethyl, isopropyl, n-propyl, iso-butyl or n-butyl;
  • the catalyst is usually and preferably used in an amount of 1 - 20 mol-equivalents (in regard to the amount of TPPO).
  • the present invention also relates to a process (P5), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’) or (P4), wherein the catalyst is used in an amount of 1-20 mol- equivalents (in regard to the amount of TPPO).
  • the process according to the present invention is carried out in at least one solvent of formula (III).
  • R 1 ’ is Ci-C2-alkyl
  • R 2 ’ is a Cs-cycloalkyl
  • R 1 ’ and R 2 ’ form (together with the O) a 5 membered ring, which can be substituted.
  • tetra hydrofuran THF
  • 2-methyltetrahydrofuran 2-MeTHF
  • CPME cyclopentyl methyl ether
  • the most preferred solvent of formula (III) is cyclopentyl methyl ether (CPME).
  • the present invention also relates to a process (P6), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4) or (P5), wherein the at least one solvent is a compound of formula (III),
  • R 1 ’ is Ci-C2-alkyl
  • R 2 ’ is a Cs-cycloalkyl
  • R 1 ’ and R 2 ’ form (together with the O) a 5 membered ring, which can be substituted.
  • the present invention also relates to a process (P6’), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4) or (P5), wherein the at least one solvent is chosen from the group consisting of tetra hydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF) or cyclopentyl methyl ether (CPME), preferably cyclopentyl methyl ether (CPME).
  • THF tetra hydrofuran
  • 2-MeTHF 2-methyltetrahydrofuran
  • CPME cyclopentyl methyl ether
  • CPME cyclopentyl methyl ether
  • the process according to the present invention is usually and preferably carried out at elevated temperature.
  • the process according to the present invention is carried out at a temperature of 80°C to 200°C, more preferably at 90°C to 180°C.
  • the present invention also relates to a process (P7), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6) or (P6’), wherein the process is carried out at a temperature of 80°C to 200°C. Therefore, the present invention also relates to a process (P7’), which is process (P1 ), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6) or (P6’), wherein the process is carried out at a temperature of 90°C to 180°C.
  • the reaction time of the process according to the present invention is usually several hours. Usually and preferably the reaction time of the process according to the present invention is 3 to 30 hours.
  • the present invention also relates to a process (P8), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6), (P6’), (P7) or (P7’), wherein the reaction time is 3 to 30 hours.
  • reaction product compound of formula (I)
  • the reaction product can also be purified (when needed) using commonly known methods.
  • the reaction was performed under nitrogen.
  • Triphenylphosphine oxide (2.76 g, 9.72 mmol) was placed in a dried 50 mL tube and CPME (20 mL, 99.8 %, ACS grade) was added. Then titanium(IV) isopropoxide (0.29 g, 0.31 mL, 1 .0 mmol) was added, followed by addition of phenyl silane (2.8 g, 3.2 mL, 2.6 Eq, 25 mmol). The tube was sealed, the mixture was heated to 125 °C for 21.25 h and analyzed by GC (A sample was taken and concentrated with rotavapor (40 °C, 10 mbar), diluted with ethyl acetate and mixed with aq. KOH (42 %). After phase separation, the organic phase was washed with sat. NaHCOs and analyzed by GC).
  • the reaction was performed under nitrogen.
  • Triphenylphosphine oxide (2.84 g, 10.0 mmol) was placed in a dried 50 mL tube and CPME (20 mL, 99.8 %, ACS grade) was added. Then titanium(IV) isopropoxide (0.29 g, 0.31 mL, 1.0 mmol) and PMHS (6.58 g, 6.50 ml, 2.58 Eq, 25.8 mmol) were added. The tube was sealed, and the mixture was heated to 125 °C for 21.25 h and analyzed by GC (A sample was taken and concentrated with rotavapor (40 °C, 10 mbar), diluted with ethyl acetate and mixed with aq. KOH (42 %). After phase separation, the organic phase was washed with sat. NaHCOs and analyzed by GC).
  • the reaction mixture was cooled to 20 °C and concentrated under reduced pressure (40 °C, 10 mbar).
  • the oily residue was diluted with pentane (20 mL) resulting in the precipitation of a colorless solid.
  • the suspension was cooled using a water bath and KOH (3 M in MeOH, 5 mL) was added. After gas evaporation stopped, the pentane phase was separated, and the methanolic phase was extracted with pentane (3 x 20 mL).
  • the pentane phases were combined, washed with sat. aq. NaHCOs (5 mL), dried with MgSO4 and concentrated under reduced pressure.
  • the product was obtained as colorless solid (2.35 g, after GC analysis: 2.27 g, 87 %).
  • Table 1 TPPO reduction experiments in presence of silanes or siloxanes and catalyst.
  • Table 2 TPPO reduction experiments in presence of silanes or siloxanes and catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to an improved process for preparing triphenylphosphine (TPP) by reacting triphenylphosphine oxide (TPPO) with a catalyst in a specific solvent (or mixture of solvents).

Description

Reduction of Triphenylphosphine Oxide
The present invention relates to an improved process for preparing triphenylphosphine (TPP) by reacting triphenylphosphine oxide (TPPO) with a catalyst in a specific solvent (or mixture of solvents).
TPP, which is the compound of formula (I)
Figure imgf000002_0001
is used on the industrial scale in the Wittig Ylide synthesis to prepare olefinic compounds such as vitamin A or carotenoids as well as in the Mitsunobu reactions.
TPP is used in stoichiometric amounts and is oxidized during these reactions to TPPO, which is the compound of formula (II)
Figure imgf000002_0002
Therefore, a lot of TPPO is produced during these reactions and unfortunately only few uses of TPPO have been disclosed. Since it is an extremely stable substance which can be disposed of only with difficulty, there have been numerous attempts to convert it back into TPP.
One common way to deal with the “TPPO-problem” is to burn the TPPO, so that it can be wasted in a secure way.
Another option is the reduction of TPPO via TPP dichloride to TPP, so that TPP can then be re-used again.
Such recycling processes are known from the prior art, e.g. from EP 638 580 A1 , from Heteroatom Chemistry 26(3), 2015, p.199 - 205. Most of these recycling processes are carried out in the presence of at least one siloxane and/or at least one silane.
Furthermore, in the present invention, at least one catalyst, which comprises as metal atom, is used as well.
The reduction of TPPO, in the state of the art, is carried out in at least one inert solvent. The solvents used for the reduction of TPPO are usually alkenes or aromatic solvents.
It was, however, found that the reduction of TPPO can be carried in specific solvents, which are green solvents and the yield of TPP is excellent.
Green solvents are environmentally friendly solvents, or biosolvents, which are derived from the processing of agricultural crops, while otherwise most of the commonly used solvents (such as alkanes or aromatic solvents) are petrochemical solvents. Green solvents are vastly more eco-friendly, less toxic, less hazardous than traditional volatile organic compounds (VOCs).
Due to the importance of the reaction, wherein the TPPO is produced (as a waste product) and the problems with the use of TPPO, there is a need for an improved way for transforming TPPO into TPP, which can then be used again and wherein no petrochemical solvents are used.
Surprisingly it was found that is possible that use of specific solvents (green solvents), allows to recycle TPPO in an excellent yield.
Therefore, the present invention relates to the process (P) for producing triphenylphosphine (compound of formula (I))
Figure imgf000003_0001
wherein triphenylphosphine oxide (the compound of formula (II))
Figure imgf000004_0001
is reacted with at least one siloxane and/or at least one silane, in the presence of at least one metal containing catalyst, and in the presence of at least one solvent of formula (III)
R1 -O— R2 (in) wherein
R1’ is Ci-C4-alkyl, and
R2’ is a C5- or a Cs-cycloalkyl, or
R1’ and R2’ form (together with the O) a 5 or 6 membered ring, which can be substituted.
If R1’ and R2’ form (together with the O) a 5 or 6 membered ring, it is preferred that said ring is not substituted.
The process according to the present invention is carried out in the presence of at least one siloxane and/or silane.
Particularly suitable siloxanes are those of formula (IV)
Figure imgf000004_0002
wherein
R1, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a Ci-C4-alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H.
Preferred siloxanes are those of formula (IV), wherein
R1, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a Ci-C2-alkyl, and m is a value from 0 to 100’000 with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H. It is preferred that Ri=H.
Particularly, it is preferred that Ri=H and R2= Rs= R4= Rs= Re= R? = Rs, preferably R2= Rs = R4 = Rs = Re = R? = Rs = ethyl or methyl, preferably methyl.
More preferred siloxanes are those of the
Figure imgf000005_0001
formulae (IV’) and (IV”)
Figure imgf000005_0002
(TMDS) and (PMHS) wherein m is a value between 2 and 100’000.
Preferably m is a value from 2 - 20’000, more preferably m is a value from 2 - 12’000, most preferably m is a value from 2 - 10’000).
Most preferred siloxane is the siloxane of the formula (IV”).
Particularly suitable silanes are those compounds of formula (Va) or (Vb) or (Vc).
Figure imgf000005_0003
wherein o is a value from 3 to 10; and Rg, R and Rn are independently from each other H or a Ci-Ce-alkyl or a OCi-Ce-alkyl or a phenyl group, with the proviso that at least one of the substituents Rg, R and Rn is different from H.
Particularly preferred silanes of formula (Vc) are silanes of the formula (Vc’) or (Vc”) or (Vc’”) or (Vc””), preferably (Vc’) or (Vc”).
Figure imgf000005_0004
(DEMS) (DMMS)
Figure imgf000006_0001
The silanes of formula (Vb) and (Vc’) and (Vc”) are the most preferred silanes.
Therefore, the present invention also relates to a process (P1), which is process (P), wherein the at least one siloxane is chosen from the group having the formula (IV)
Figure imgf000006_0002
wherein
Ri, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a Ci-C4-alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H. Therefore, the present invention also relates to a process (PT), which is process (P1), wherein the at least one siloxane is chosen from the group having the formula (IV), Wherein R1, R2, R3, R4, Rs, Re, R7 and Rs are independently from each other H or a C1-C2- alkyl, and m is a value from 0 to 100’000; with the proviso that at least one of the substituents R1, R2, R3, R4, Rs, Re, R7 or Rs is H.
Therefore, the present invention also relates to a process (P1”), which is process (P1), wherein the at least one siloxane is chosen from the group consisting of
Figure imgf000006_0003
(TMDS) and (PMHS) wherein m is a value between 10 and 100’000 (preferably m is a value from 100 - 20’000, more preferably m is a value from 1000 - 12’000, most preferably m is a value from 1000 - 10’000).
Therefore, the present invention also relates to a process (P2), which is process (P1), (PT) or (P1 ”), wherein the at least one silane is chosen from the group having the formula (Va) and (Vb) and (Vc)
Figure imgf000007_0001
wherein o is a value from 3 to 10; and Rg, R and Rn are independently from each other H or a Ci-Ce-alkyl or a OCi-Ce-alkyl or a phenyl group, with the proviso that at least one of the substituents Rg, R and Rn is different from H.
Therefore, the present invention also relates to a process (P2’), which is process (P1), (PT) or (P1 ”), wherein the at least one silane is
Figure imgf000007_0002
In the process according to the present invention, the at least one siloxane and/or the at least one silane is usually and preferably used in an amount of 1 - 10 mol-%, preferably 2 - 8 mol-%, in regard to the compound of formula (II).
Therefore, the present invention also relates to a process (P3), which is process (P1), (PT), (P1 ”), (P2) or (P2’), wherein the at least one siloxane and/or the at least one silane is used in an amount of 1 - 10 mol-%, in regard to the compound of formula (II).
Therefore, the present invention also relates to a process (P3’), which is process (P1), (PT), (P1 ”), (P2) or (P2’), wherein the at least one siloxane and/or the at least one silane is used in an amount of 2 - 8 mol-%, in regard to the compound of formula (II). The process according to the present invention is carried out in the presence of at least one catalyst, which comprises at least one metal atom. Such catalysts are known from the prior art. Suitable catalysts comprise at least one metal atom, wherein the metal is chosen from the group consisting of Ti, Cu, Ni and In.
Suitable catalysts are those of formula (VI)
R6'
R3'— Ti - R5' (VI)
R4' wherein
R3’, R4’, R5’ and R6’ are independently from each other OR7’, wherein R7’ is a linear or branched Ci - Ce alkyl group, preferably ethyl, iso-propyl, n-propyl, iso-butyl or n-butyl; or
Cu(OTf)2, or InBrs.
Therefore, the present invention also relates to a process (P4), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3) or (P3’), wherein the at least one catalyst is chosen from the group consisting of compounds of formula (VI)
R6'
R3'— Ti - R5' (VI)
R4' wherein
R3’, R4’, R5’ and R6’ are independently from each other OR7’, wherein R7’ is a linear or branched Ci - Ce alkyl group, preferably R7 is ethyl, isopropyl, n-propyl, iso-butyl or n-butyl;
Cu(OTf)2, and InBrs.
In the process according to the present invention the catalyst is usually and preferably used in an amount of 1 - 20 mol-equivalents (in regard to the amount of TPPO).
Therefore, the present invention also relates to a process (P5), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’) or (P4), wherein the catalyst is used in an amount of 1-20 mol- equivalents (in regard to the amount of TPPO). The process according to the present invention is carried out in at least one solvent of formula (III).
Preferred are solvents of formula (III)
R1'— 0— R2 (Hi) wherein
R1’ is Ci-C2-alkyl, and
R2’ is a Cs-cycloalkyl, or
R1’ and R2’ form (together with the O) a 5 membered ring, which can be substituted.
Most preferred are tetra hydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF) or cyclopentyl methyl ether (CPME). The most preferred solvent of formula (III) is cyclopentyl methyl ether (CPME).
Therefore, the present invention also relates to a process (P6), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4) or (P5), wherein the at least one solvent is a compound of formula (III),
R1 -O— R2 (in) wherein
R1’ is Ci-C2-alkyl, and
R2’ is a Cs-cycloalkyl, or
R1’ and R2’ form (together with the O) a 5 membered ring, which can be substituted.
Therefore, the present invention also relates to a process (P6’), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4) or (P5), wherein the at least one solvent is chosen from the group consisting of tetra hydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF) or cyclopentyl methyl ether (CPME), preferably cyclopentyl methyl ether (CPME).
The process according to the present invention is usually and preferably carried out at elevated temperature. Preferably, the process according to the present invention is carried out at a temperature of 80°C to 200°C, more preferably at 90°C to 180°C.
Therefore, the present invention also relates to a process (P7), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6) or (P6’), wherein the process is carried out at a temperature of 80°C to 200°C. Therefore, the present invention also relates to a process (P7’), which is process (P1 ), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6) or (P6’), wherein the process is carried out at a temperature of 90°C to 180°C.
The reaction time of the process according to the present invention is usually several hours. Usually and preferably the reaction time of the process according to the present invention is 3 to 30 hours.
Therefore, the present invention also relates to a process (P8), which is process (P1), (PT), (P1 ”), (P2), (P2’), (P3), (P3’), (P4), (P5), (P6), (P6’), (P7) or (P7’), wherein the reaction time is 3 to 30 hours.
After the process the reaction product (compound of formula (I)) is isolated using commonly known methods. The reaction product can also be purified (when needed) using commonly known methods.
Examples
The following examples illustrate the invention.
Example 1
The reaction was performed under nitrogen.
Triphenylphosphine oxide (2.76 g, 9.72 mmol) was placed in a dried 50 mL tube and CPME (20 mL, 99.8 %, ACS grade) was added. Then titanium(IV) isopropoxide (0.29 g, 0.31 mL, 1 .0 mmol) was added, followed by addition of phenyl silane (2.8 g, 3.2 mL, 2.6 Eq, 25 mmol). The tube was sealed, the mixture was heated to 125 °C for 21.25 h and analyzed by GC (A sample was taken and concentrated with rotavapor (40 °C, 10 mbar), diluted with ethyl acetate and mixed with aq. KOH (42 %). After phase separation, the organic phase was washed with sat. NaHCOs and analyzed by GC).
The reaction mixture was cooled to 20 °C and concentrated under reduced pressure (40 °C, 10 mbar). The oily residue was diluted with pentane (20 mL) resulting in the precipitation of a colorless solid. The suspension was cooled using a water bath and KOH (3 M in MeOH, 5 mL) was added. After gas evaporation stopped, the pentane phase was separated, and the methanolic phase was extracted with pentane (3 x 20 mL). The pentane phases were combined, washed with sat. aq. NaHCOs (5 mL), dried with MgSO4 and concentrated under reduced pressure. The product was obtained as colorless solid (2.35 g, after GC analysis: 2.22 g, 87 %). Example 2
The reaction was performed under nitrogen.
Triphenylphosphine oxide (2.84 g, 10.0 mmol) was placed in a dried 50 mL tube and CPME (20 mL, 99.8 %, ACS grade) was added. Then titanium(IV) isopropoxide (0.29 g, 0.31 mL, 1.0 mmol) and PMHS (6.58 g, 6.50 ml, 2.58 Eq, 25.8 mmol) were added. The tube was sealed, and the mixture was heated to 125 °C for 21.25 h and analyzed by GC (A sample was taken and concentrated with rotavapor (40 °C, 10 mbar), diluted with ethyl acetate and mixed with aq. KOH (42 %). After phase separation, the organic phase was washed with sat. NaHCOs and analyzed by GC).
The reaction mixture was cooled to 20 °C and concentrated under reduced pressure (40 °C, 10 mbar). The oily residue was diluted with pentane (20 mL) resulting in the precipitation of a colorless solid. The suspension was cooled using a water bath and KOH (3 M in MeOH, 5 mL) was added. After gas evaporation stopped, the pentane phase was separated, and the methanolic phase was extracted with pentane (3 x 20 mL). The pentane phases were combined, washed with sat. aq. NaHCOs (5 mL), dried with MgSO4 and concentrated under reduced pressure. The product was obtained as colorless solid (2.35 g, after GC analysis: 2.27 g, 87 %).
Additional experiments are summarized in the following table. The same reactions conditions are used as in Example 1 when not otherwise listed in the table 1 .
Table 1 : TPPO reduction experiments in presence of silanes or siloxanes and catalyst.
Figure imgf000011_0001
Table 2: TPPO reduction experiments in presence of silanes or siloxanes and catalyst.
Figure imgf000011_0002

Claims

Claims
1. Process for producing triphenylphosphine (compound of formula (I))
Figure imgf000012_0001
is reacted with at least one siloxane and/or at least one silane, in the presence of at least one metal containing catalyst, and in the presence of at least one solvent of formula (III)
R1 -O— R2 (in) wherein
R1’ is Ci-C4-alkyl, and
R2’ is a Cs- or a Ce-cycloalkyl, or
R1’ and R2’ form (together with the O) a 5 or 6 membered ring, which can be substituted.
2. Process according to claim 1 , wherein the at least one siloxane is chosen from the group consisting of
Figure imgf000012_0002
(TMDS) and (PMHS) wherein m is a value between 2 and 100’000, preferably m is a value from 2 - 20’000, more preferably m is a value from 2 - 12’000, most preferably m is a value from 2 - 10’000.
3. Process according to claim 1 or claim 2, wherein the at least one silane is chosen from the group having the formula (Va) and (Vb) or (Vc)
Figure imgf000013_0001
wherein o is a value from 3 to 10 and Rg, R and Rn are independently from each other H or a Ci-Ce-alkyl or a OCi-Ce-alkyl or a phenyl group, with the proviso that at least one of the substituents Rg, R and Rn is different from H.
4. Process according to claim 3, characterized in that the silane of the formula (Vc) is a silane of the (Vc’) or (Vc”) or (Vc’”) or (Vc””), preferably (Vc’) or (Vc”)
Figure imgf000013_0002
5. Process according to any of the preceding claims, wherein the at least one siloxane and/or the at least one silane is used in an amount of 1 - 10 mol-%, preferably 2 - 8 mol- %, in regard to the compound of formula (II).
6. Process according to any of the preceding claims, wherein the at least one catalyst is chosen from the group consisting of compounds of formula (VI)
R6'
R3'— Ti - R5' (VI)
R4' wherein
R3’, R4’, R5’ and R6’ are independently from each other OR7’, wherein R7’ is a linear or branched Ci - Ce alkyl group, preferably R7 is ethyl, isopropyl, n-propyl, iso-butyl or n-butyl;
Cu(OTf)2, and InBrs.
7. Process according to any of the preceding claims, wherein the catalyst is used in an amount of 1-20 mol-equivalents, in regard to the amount of TPPO.
8. Process according to any of the preceding claims, wherein the at least one solvent is a compound of formula (III),
R1'— 0— R2 (Hi) wherein
R1’ is Ci-C2-alkyl, and
R2’ is a Cs-cycloalkyl, or
R1’ and R2’ form (together with the O) a 5 membered ring, which can be substituted.
9. Process according to any of the preceding claims, wherein the at least one solvent is chosen from the group consisting of tetra hydrofuran (THF), 2-methyltetrahydrofuran (2- MeTHF) or cyclopentyl methyl ether (CPME), preferably cyclopentyl methyl ether (CPME).
10. Process according to any of the preceding claims, wherein the process is carried out at a temperature of 80°C to 200°C.
11. Process according to any of the preceding claims, wherein the reaction time is 3 to
30 hours.
PCT/EP2023/084140 2022-12-05 2023-12-04 Reduction of triphenylphosphine oxide WO2024121062A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22211318 2022-12-05
EP22211318.5 2022-12-05

Publications (1)

Publication Number Publication Date
WO2024121062A1 true WO2024121062A1 (en) 2024-06-13

Family

ID=84602491

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/084140 WO2024121062A1 (en) 2022-12-05 2023-12-04 Reduction of triphenylphosphine oxide

Country Status (1)

Country Link
WO (1) WO2024121062A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0638580A1 (en) 1993-08-11 1995-02-15 BASF Aktiengesellschaft Process for the preparation of triphenyl phosphine
FR2932181A1 (en) * 2008-06-05 2009-12-11 Rhodia Operations Reduction of a functional group containing phosphorus atom in a substrate, comprises placing the substrate in the presence of a siloxane type compound associated with a base catalyst of a metal element

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0638580A1 (en) 1993-08-11 1995-02-15 BASF Aktiengesellschaft Process for the preparation of triphenyl phosphine
FR2932181A1 (en) * 2008-06-05 2009-12-11 Rhodia Operations Reduction of a functional group containing phosphorus atom in a substrate, comprises placing the substrate in the presence of a siloxane type compound associated with a base catalyst of a metal element

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
COUMBE T ET AL: "Titanium (IV) catalysis in the reduction of phosphine oxides", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM , NL, vol. 35, no. 4, 1 January 1994 (1994-01-01), pages 625 - 628, XP026646244, ISSN: 0040-4039, [retrieved on 19940101], DOI: 10.1016/S0040-4039(00)75855-2 *
HETEROATOM CHEMISTRY, vol. 26, no. 3, 2015, pages 199 - 205
LAYE CLAIRE ET AL: "The Trityl-Cation Mediated Phosphine Oxides Reduction", vol. 363, no. 12, 3 May 2021 (2021-05-03), pages 3035 - 3043, XP093040659, ISSN: 1615-4150, Retrieved from the Internet <URL:https://onlinelibrary.wiley.com/doi/full-xml/10.1002/adsc.202100189> DOI: 10.1002/adsc.202100189 *

Similar Documents

Publication Publication Date Title
US4960916A (en) Organometallic antimony compounds useful in chemical vapor deposition processes
JPH0474282B2 (en)
Hudeczek et al. Paramagnetic decamethylbimetallocenes
Hunger et al. Reactions of cyclopentadienylmolybdenum compounds with bismuth alkoxides
Kavaliunas et al. Preparation of highly reactive metal powders. Direct reaction of nickel, cobalt, and iron metal powders with arene halides
US20030139617A1 (en) Fullerene derivatives and their metal complexes
US3170958A (en) Mono-and di-secondary aliphatic ethers
WO2024121062A1 (en) Reduction of triphenylphosphine oxide
EP0147472B1 (en) 4-chloro-4-methyl-5-methylene-1,3-dioxolan-2-one
EP0648215B1 (en) Process for the preparation of trialkyl compounds of group 3a metals
GB2160202A (en) Preparation of tamoxifen
EP0590539B1 (en) Processes for producing tetrathiafulvalene derivatives and their precursors
EP0267066B1 (en) Organomagnesium compounds in solid form, process for their preparation and their use
WO2024121063A1 (en) Reduction of triphenylphosphine oxide with specific catalyst
US3297756A (en) Cyclononatetraenide salts and process of preparing
US4278611A (en) Process for synthesizing alkoxyalanates of alkaline earth metals
US3511879A (en) Cyclobutene imines and allene amidines and preparation thereof
KR890004126B1 (en) Process for preparing n-aryl-halopyrolidones
KR800000644B1 (en) Method of preparing alpha-vinyloxazolines
JPS6111230B2 (en)
EP0093467B1 (en) Process for preparing 1,1,3,3-tetramethyl-2,3-dihydro-1-h-isoindoles substituted in position 5 and/or 6
KR20240073969A (en) Method for producing organo-titanium compounds
Yagupolskii et al. N, N-Bis (difluoromethyl) anilines
JP2021178811A (en) Production method of aromatic ether compound or aromatic sulfhydryl compound
JP2023127737A (en) Compound, and production method of the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23813421

Country of ref document: EP

Kind code of ref document: A1