WO2017088987A1 - Sélénodiphénols protégés et leurs procédés de production - Google Patents

Sélénodiphénols protégés et leurs procédés de production Download PDF

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WO2017088987A1
WO2017088987A1 PCT/EP2016/054419 EP2016054419W WO2017088987A1 WO 2017088987 A1 WO2017088987 A1 WO 2017088987A1 EP 2016054419 W EP2016054419 W EP 2016054419W WO 2017088987 A1 WO2017088987 A1 WO 2017088987A1
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alkyl
aryl
substituted
groups
substituent
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PCT/EP2016/054419
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German (de)
English (en)
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Katrin Marie DYBALLA
Robert Franke
Detlef Selent
Armin BÖRNER
Claudia WEILBEER
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Evonik Degussa Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Definitions

  • Novel selenodiphenols protected at least one hydroxyl group, as well as processes for their preparation and their use as ligands in complexes.
  • TK Paine et al describes a synthesis of 2,2 " - selenobis (4,6-di-tert-butylphenol) using selenium dioxide.
  • the preparation of 2,2 " -selenobis (4,6-di-tert-butylphenol) takes place here in an acidic medium with the addition of concentrated hydrochloric acid The product is obtained in a yield of only 25%.
  • the object of the invention was to produce a further completely new class of ligand building blocks in order to expand the field of available ligands for the respective specific complexes in catalysis. Furthermore, the task of producing ligands for rhodium hydroformylation catalysts. Therefore, it was also the object to provide new ligand building blocks, which serve as an intermediate for the preparation of ligands.
  • the objects are achieved by simple and / or doubly protected on the two hydroxyl groups selenodiphenols.
  • the objects are achieved by the selenobiaryls of the general structure Ia and the structures Ib and / or Ic, as well as mixtures containing Ia, Ib and Ic or two of said selenobiaryl.
  • the invention relates to compounds of the selenodiaryl of the general structure Ia and compositions obtainable by the process according to the invention,
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each independently selected from: -H, - (Ci-Ci 2 ) -alkyl, -0- (ci Ci 2 ) -alkyl, - (C6-C 2 o) -aryl, -O- (C6-C 2 o) -aryl, -halogen,
  • -OC 0- (Ci-Ci 2) -alkyl, -S-alkyl, -S-aryl, -COO- (Ci-Ci2) alkyl, -CONH- (Ci-Ci 2) -alkyl, -CO - (Ci-Ci 2 ) -alkyl, -CO- (C6-C 2 o) -aryl, -COOH, -S0 3 H, -CN, -N [(Ci-Ci 2 ) -alkyl] 2 , wherein the Alkyl and aryl groups may each be independently unsubstituted or substituted, substituted - (Ci-Ci2) alkyl groups and substituted - (C6-C2o) aryl groups may, depending on their chain length, one or more substituents exhibit; the substituents are independently selected from
  • R 5 and R 10 are each independently selected from:
  • alkyl and aryl groups are each independently unsubstituted or substituted - (C 1 -C 12) -alkyl groups and substituted - (C 6 -C 20) -aryl groups, depending on their chain length, may have one or more substituents; the substituents may be independently selected from among
  • R 5 and R 10 are each independently selected from: -methylthioethyl, -trimethylsilyl, -triethylsilyl, -triisopropylsilyl, -ie / f.-butyldimethylsilyl, -ie / f.-butyldiphenylsilyl, -acetyl, -pivaloyl, -benzoic acid ester, - 3 (2-nitrophenyl) acetyl, oxoacyl, trifluoromethanesulfonyl,
  • R 5 and R 10 are unequal when R 5 or R 10 is -H.
  • the situation R 5 and R 10 equal to -H are excluded from the invention.
  • selenodiaryl, selenodiphenol, phenol and olefin are used in this application as a generic term and thus each include thus also substituted selenodiaryl, selenodiphenols, phenols and olefins.
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each independently selected in the selenodiaryls of structures Ia, Ib, Ic and in the selenodiphenols of structure II from: -H, unsubstituted - (Ci-Ci2) -alkyl and / or unsubstituted -0- (Ci-Ci2) -alkyl groups, whereby the alkyl groups can be linear, branched or cyclisch.
  • One or more substituents preferably comprise 1 to 10 substituents, in particular 1 to 3.
  • - (C 1 -C 12) -alkyl comprises straight-chain and branched alkyl groups. These are preferably unsubstituted straight-chain or branched - (C 1 -C 5) -alkyl groups and, most preferably, - (C 1 -C 6) -alkyl groups.
  • Examples of - (C 1 -C 12) -alkyl groups are, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl,
  • Halogen includes chlorine, bromine and iodine, with chlorine and fluorine being particularly preferred.
  • Substituted - (Ci-Ci2) alkyl groups and substituted - (Ci-Ci2) alkoxy groups can, depending on their chain length, have one or more substituents.
  • the substituents can be preferably independently selected from - (C6-C2o) -aryl, such as - (Ci-Ci2) alkyl- (C6-C2o) -aryl, - (C 3 -C 2) cycloalkyl .
  • the substituents - (Ci-Ci2) alkyl (C6-C2o) aryl correspond substituted with aryl groups alkyl groups so alkylaryl groups such as benzyl, or substituted with alkyl groups benzyl derivatives such as - (Ci-Ci2) alkyl (C 6 -C 20) -aryl, where aryl may be substituted by at least one - (C 1 -C 12) -alkyl.
  • - (C6-C 2 o) aryl, and - (C6-C2o) aryl (C 6 -C2o) aryl or - (C6-C 2 o) aryl (Ci-Ci2) - alkyl in the context of the present invention comprises mono- or polycyclic aromatic hydrocarbon radicals. These have 6 to 20 ring atoms, more preferably 6 to 14 Ring atoms, in particular 6 to 10 ring atoms, on.
  • Aryl is preferably - (C 6 -C 10) -aryl and - (C 6 -C 10) -aryl- (C 6 -C 10) -arykyl
  • Aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl , Coronene.
  • aryl is phenyl, naphthyl and antracenyl.
  • - (C 3 -C 12) -cycloalkyl in the context of the present invention comprises mono-, bi- or tricyclic hydrocarbon radicals having 3 to 12, in particular 5 to 12, carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbonyl or adamantyl.
  • An example of a substituted cycloalkyl would be menthyl.
  • - (C 3 -C 12) -heterocycloalkyl groups in the context of the present invention comprises non-aromatic, saturated or partially unsaturated cycloaliphatic groups having 3 to 12, in particular 5 to 12, carbon atoms.
  • the - (C 3 -C 12) -heterocycloalkyl groups preferably have 3 to 8, more preferably 5 or 6, ring atoms.
  • the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups.
  • - (C 3 -C 12) -heterocycloalkyl groups include tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and dioxanyl.
  • Compounds according to the invention include mono- and / or diethers of selenodiphenols and mixtures thereof.
  • selenodiaryl of the structure Ia where R 5 and R 10 are each independently selected from -H, - (C 1 -C 12) -alkyl-O- (C 1 -C 12) -alkyl, - (Ci-Ci2) alkyl-0- (C 6 -C2o) aryl, - (Ci-Ci2) alkyl- (C 6 -C2o) -aryl, - (C6-C2o) -aryl (C 1 -C 12) -alkyl, - (C 1 -C 12) -alkyl-O- (C 1 -C 12) -alkyl- (C 6 -C 20) -aryl, -trimethylsilyl, where R 5 and R 10 are not identical, when R 5 or R 10 is -H.
  • Ci2 alkyl- (C6-C2o) -aryl, - (Ci-Ci2) alkyl-0- (C6-C2o) -aryl, wherein R 5 and R are not equal to 10 when R 5 or R 10 equals -H.
  • Particularly preferred are selenodiaryl of the structure Ia, with R 5 and R 10 each independently selected from -H, methoxymethyl, benzyl, wherein R 5 and
  • R 10 are unequal when R 5 or R 10 is -H.
  • the compound is selected from
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each, in particular within the respective
  • alkyl and aryl groups may each independently be unsubstituted or substituted, substituted - (Ci-Ci2) alkyl groups and substituted - (C6-C2o) aryl groups may, depending on their chain length, one or more substituents exhibit; the substituents are independently selected from - (C 3 -C 2) cycloalkyl, - (C 3 -C 2) -heterocycloalkyl, - (C 6 -C2o) aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl or wherein the respective radical R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9, although independently selected, is the same in the structures Ia, Ib and / or Ic, and
  • R 5 and R 10 are the same and are selected from:
  • alkyl and aryl groups are each independently unsubstituted or substituted, substituted - (C 1 -C 12) alkyl groups and substituted - (C 6 -C 20) aryl groups, depending on their chain length, may have one or more substituents; the substituents can be independently selected from - (C 3 -C 12) -cycloalkyl, - (C 3 -C 12) -heterocycloalkyl, - (C 6 -C 20) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl; likewise, R 5 and R 10 according to the invention may each be independently selected from:
  • R 5 equal to R 10 is selected in structure la and R 5 and R 10 are selected from - (Ci-Ci2) alkyl-0- (Ci-Ci2) alkyl, - (C 1 -C 12) -alkyl- (C 6 -C 20) -aryl, - (C 6 -C 20) -aryl (C 1 -C 12) -alkyl, - (C 1 -C 12) -alkyl-O- (C 6 -C 2 o) -aryl,
  • R 5 is equal to R 10 are selected in structure la and R 5 and R 10 are selected
  • R 5 is R 10 and is selected from methoxymethyl (-CH 2 OCH 3 (MOM)), -CH 2 OCH 2 C 6 H 5 (BOM), -CH 2 OCH 2 CH 2 OCH 3 (MEM), benzyl.
  • R 5 is R 10 in structure Ia and R 5 and R 10 are selected from methylthioethyl, trimethylsilyl,
  • R 5 is R 10 in structure Ia and R 5 and R 10 is trimethylsilyl.
  • the invention provides a compound of a selenodiaryl
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 in structures Ia, Ib and / or Ic are each independently selected from: -H, - ( Ci-Ci 2 ) -alkyl, -0- (Ci-Ci 2 ) -alkyl, - (C 6 -C 2 o) -aryl and -0- (C6-C 2 o) -aryl, wherein said alkyl groups unsubstituted or substituted as defined above, in particular in the alternatives a), b), c) and / or d).
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 in the structures Ia, Ib and / or Ic are each independently selected from -H, - (Ci-Ci2) Alkyl, -0- (Ci-Ci2) alkyl, preferably
  • R 1 , R 3 , R 6 , R 8 in the structures Ia, Ib and / or Ic are each independently selected from -H, - (Ci-Ci2) alkyl, in particular - (Ci-C4 ) Alkyl, wherein said alkyl groups may be unsubstituted or substituted.
  • R 1 , R 3 , R 6 , R 8 in the structures Ia, Ib and / or Ic are each independently methyl, ethyl, ie / f-butyl and / or isopentyl and R 2 , R 4 , R 7 and R 9 are equal to -H.
  • the abovementioned selenodiarylics according to embodiments a), b), c) and d) are correspondingly substituted.
  • R 1 , R 3 , R 6 , R 8 in the structures Ia, Ib and / or Ic are methyl, preferably R 2 , R 4 , R 7 , and R 9 are -H.
  • R 1 , R 3 , R 6 , R 8 in the structures Ia, Ib and / or Ic are tert-butyl, wherein preferably R 2 , R 4 , R 7 , and R 9 are -H.
  • R 1 , R 6 in the structures Ia, Ib and / or Ic are tert-butyl, wherein preferably R 2 , R 3 , R 4 , R 7 , R 8 and R 9 are -H.
  • R 3 , R 8 in the structures Ia, Ib and / or Ic are methyl, preferably R 1 , R 2 , R 4 , R 6 , R 7 and R 9 are -H.
  • the invention likewise provides a process for the preparation of selenodiarylenes of the general structure Ia, in particular of the general structures Ia, Ib and Ic, and the compounds and compositions obtainable by the process, the process comprising the process steps,
  • R 5 and R 10 in formulas IIIa and IIIb are each independently selected from:
  • R 5 and R 10 may each be independently selected from: methylthioethyl, trimethyl
  • alkyl and aryl groups may each independently be unsubstituted or substituted, substituted - (C 1 -C 12) alkyl groups and substituted - (C 6 -C 20) aryl groups may have one or more substituents depending on their chain length; the substituents may be independently selected from - (C 3 -C 2) cycloalkyl, - (C 3 -C 2) -heterocycloalkyl, - (C6-C2o) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, in particular R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each independently selected but identical in structures II and la,
  • R 5 and R 10 in structure Ia are each independently selected from: -H, - (Ci-Ci2) alkyl-0- (Ci-Ci2) alkyl, - (Ci-Ci2) alkyl- (C6-C 2 o) aryl,
  • Y in YR 5 of the formula IIa and / or in YR 10 as the cleavable radical Y can correspond to one of the following cleavable radicals, without these radicals being limited to those listed.
  • Y may include: shark, organyl, acyl, carboxy, carbonyl.
  • all radicals known to the person skilled in the art in protecting group chemistry can be used as cleavable radicals Y.
  • the choice of Y is known to the person skilled in the art, since the compound YR 5 of the formula IIIa and / or YR 10 of the formula IIIb is used to introduce the group R 5 or R 10 and Y represents the counterpart.
  • the introduction of R 5 or R 10 Me called.
  • methylating reagent For example, methyl iodide or dimethyl sulfate in question, so that Y is iodide or sulfate.
  • Y as a cleavable group thus also represents a counterion which is negatively charged or carries a negative partial charge. Accordingly, this counterion has a negative oxidation number.
  • the compounds comprising the protecting groups R 5 and R 10 may be the same, such that YR 5 may be lilac and / or YR 10 lllb, where Y is halogen selected from chlorine, bromine and iodine, in particular Y is the same chlorine, and R 5 and R 10 are identical and are selected from - (Ci-Ci2) alkyl-0- (Ci-Ci 2) -alkyl and - (Ci-Ci2) alkyl- (C6-C 2 o) aryl,
  • the selenodiphenol II can be reacted with YR 5 of the formula IIIa and / or YR 10 of the formula IIIb in a molar ratio of 10: 1 to 1:10, preferably from 5: 1 to 1: 5.
  • the selenodiphenol can be particularly preferred II with 0.8 to 1.2 eq (equimolar), in particular 0.9 to 1.1 eq, of the YR 5 formula IIIa and / or YR 10, formula IIIb, where preferably formula IIIa is equal to IIIb.
  • a reaction of about 1 mol of selenodiphenol with about greater than or equal to 2 moles of YR 5 formula IIIa and / or YR 10 formula IIIb each with +/- 0.2 mol for preparing the compound Ia with R 5 is R 10 , and wherein R 5 is R 10 is not -H, preferred according to a process alternative.
  • a selenodiphenol of general structure II can be converted to selenodiaryls of structures Ia and / or Ib by reacting about 1 mol of selenodiphenol II with about 0.8 to 1.2 moles of YR 5 formula IIIa and / or YR 10 Formula IIIb is implemented.
  • the reaction can be carried out by reacting the selenodiphenol of the general structure II in the presence of a strong base selected from metal hydrides sodium hydride, lithium hydride, lithium organyls such as n-butyllithium, alkylamines such as triethylamine, pyridine bases, in particular metal hydrides with YR 5 purple and YR 10 lllb with Y being halogen selected from chlorine, bromine and iodine, and R 5 and R 10 are selected from - (Ci-Ci2) alkyl, - (Ci-Ci2) alkyl-0- (Ci-Ci 2 ) -alkyl, - (C6-C2o) -aryl, in particular of the formula YR 5 purple and YR 10 of formula IIIb same.
  • a strong base selected from metal hydrides sodium hydride, lithium hydride, lithium organyls such as n-butyllithium, alkylamines such as
  • X is particularly preferably equal to chlorine
  • R 5 and R 10 are selected from - (Ci-Ci2) alkyl, - (Ci-Ci2) alkyl-0- (Ci-Ci2) alkyl, - (C6- C 2 o) -aryl, particularly preferred are - (C 1 -C 4) -alkyl, - (C 1 -C 4) -alkyl-O- (C 1 -C 4) -alkyl, preferably methoxymethyl, benzyl, methyl, ie / f.-butyl.
  • the following compounds may preferably also be obtained by the process, which are selected from selenodiaryls of structures Ia, Ib and Ic or mixtures containing at least two of structures Ia, Ib and Ic, such as Ia and Ic, Ia and Ib; Ib and Ic,
  • R 5 is R 10 in structure Ia
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each independently selected from: -H, - (Ci-Ci 2 ) -alkyl, -0- (ci Ci 2 ) -alkyl, - (C 6 -C 20) -aryl, -O- (C 6 -C 20) -aryl, -halogen,
  • -OC 0- (Ci-Ci 2) -alkyl, -S-alkyl, -S-aryl, -COO- (Ci-Ci2) alkyl, -CONH- (Ci-Ci 2) -alkyl, -CO - (Ci-Ci 2) -alkyl, CO- (C6-C2o) aryl, -COOH, -S0 3 H, -CN, -N [(Ci-Ci2) alkyl] 2; wherein the alkyl and aryl groups may each independently be unsubstituted or substituted, substituted - (C 1 -C 12) alkyl groups and substituted - (C 6 -C 20) aryl groups may have one or more substituents depending on their chain length; the substituents may be independently selected from among
  • R 5 and R 10 are the same and are selected from:
  • R 5 and R 10 may each be independently selected from: methylthioethyl, trimethylsilyl, triethylsilyl,
  • R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are each independently selected and R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 are the same in the respective structures Ia, Ib and Ic.
  • the invention further provides a complex comprising at least one compound of general structure Ia, Ib and / or Ic or of mixtures comprising at least two of said structures, and at least one metal atom selected from Rh, Ru, Co, Ir, in particular Rh, Ir, Ru, preferably Rh.
  • the complexes may be present as simple complexes or dimers, etc.
  • Preferred is a complex comprising at least one compound of the general structure Ia wherein R 5 and R 10 are not -H, and R 5 and R 10 otherwise correspond to the abovementioned definitions, preferably with R 5 equal to R 10 .
  • the invention likewise provides for the use of at least one compound of the general structure Ia, Ib and / or Ic or of mixtures comprising at least two of said structures as ligand in a complex comprising at least one meta IIatom.
  • the invention provides the use of at least one compound of general structure Ia, Ib and / or Ic or of mixtures comprising at least two of the cited hydroformylation reaction structures, particularly preferred is the use of a compound the structure Ia, wherein R 5 and R 10 are not -H and R 5 and R 10 otherwise correspond to the abovementioned definitions, preferably with R 5 equal to R 10 .
  • the invention likewise relates to the use of a compound of general structure Ia, in particular of structures Ib and / or Ic, as an intermediate for the preparation of ligands, such as phosphite-protected selenodiphenols in which R 5 or R 10 corresponds to an unsubstituted or substituted phosphite group which carries, for example, a phenol or biphenol unit.
  • ligands such as phosphite-protected selenodiphenols in which R 5 or R 10 corresponds to an unsubstituted or substituted phosphite group which carries, for example, a phenol or biphenol unit.
  • the subject matter of the invention is a method comprising the method steps
  • olefin is reacted to an aldehyde.
  • the process steps (i), (ii), (iii) and (iv) may alternatively be carried out in any order.
  • a yield of greater than or equal to 85% and / or an n-regioselectivity of greater than 20% can preferably be achieved with the compounds according to the invention of the structures Ia, Ib and / or Ic in a hydroformylation according to the above use or the above process.
  • the invention will be explained in more detail by way of examples, without limiting the invention to the exemplary embodiments.
  • Solvents for extraction and column chromatography were used in the following purities: dichloromethane (99.9%, Walter, Art. No. BIE 073107033), ethyl acetate (99.5%, Walter, Art. No. BIE 003917025) and n-hexane ( 95%, Walter (Baker), Item No. 8669), n-heptane (95%, Walter (Baker), Item No. 8662).
  • Other solvents for extraction and column chromatography were of technical grade and were used without further purification unless otherwise stated.
  • IR spectroscopy The IR spectra were recorded using the Nicolet 6700 FT-IR spectrometer from Thermo Electron. The substances were measured by ATR method.
  • 77 Se NMR spectroscopy The 77 Se NMR spectra were recorded on the Bruker AV 300 (57 MHz). The spectra were measured 1 H broadband decoupled. The chemical shifts are indicated in ppm.
  • the hydroformylation was carried out in a 200 mL autoclave from Premex Reactor AG, Lengau, Switzerland, equipped with pressure maintenance, gas flow measurement, gassing stirrer and pressure pipette.
  • the toluene solvent was purified with a Pure Solv MD-7 system and stored under argon.
  • the substrate 1-octene or n-octene used as substrate (EVONIK Industries AG, octene isomer mixture of 1-octene: 3.3%, cis + trans-2-octene: 48.5%, cis + trans-3-octene: 29.2%; cis + trans-octene-4: 16.4%, skeletally isomer octene: 2.6%) was refluxed for several hours over sodium and distilled under argon.
  • the initial volume of the catalyst solution was adjusted to 41.0 ml.
  • 1-octene and n-octenes (10.70 g).
  • the synthesis gas pressure was increased to a) 48.5 bar for a final pressure of 50 bar or b) 19.5 bar for a final pressure of 20 bar and the educt was pressurized with an overpressure of about 3 bar set in the pressure pipette.
  • the reaction was carried out at a constant pressure of 50 or 20 bar (post-pressure regulator from Bronkhorst, NL) for 4 h.
  • the autoclave was cooled to room temperature at the end of the reaction time, expanded with stirring and purged with argon.
  • reaction mixtures were removed immediately after switching off the stirrer, diluted with 5.0 mL of pentane and analyzed by gas chromatography: HP 5890 Series II plus, PONA, 50 mx 0.2 mm x 0.5 ⁇ .
  • Example 1 2.0 eq of sodium hydride (60% in paraffin oil) in 3.0 mL of abs. H 2 O were added to a 25 mL Schlenk vessel under argon atmosphere. DMF suspended and cooled to 0 ° C. Subsequently, 1 .0 eq selenodiphenol II, dissolved in 2.0 mL abs. DMF, added dropwise. The resulting yellowish solution was stirred at 0 ° C for ten minutes and at RT for one hour. Subsequently, again at 0 ° C, 2.0 eq of the halide and stirred for 10 minutes at 0 ° C, with a turbidity of the reaction solution was observed.
  • the resulting yellowish oil was taken up in acetonitrile (5.0 mL / 1.0 mmol) and treated with n-heptane (2.5 mL / 1 .0 mmol). The phases were separated and the solvent removed under reduced pressure. The crude product was dried in vacuo at 50 ° C for three hours.
  • Example 2 As in Example 1, 81.0 mg (2.03 mmol, 2.0 eq, 60% in paraffin oil) of sodium hydride and 548 mg (1.70 mmol, 1.0 eq) of selenodiphenol II were reacted with 153 ⁇ (301 mg, 3.74 mmol, 2.0 eq) of chlorodimethyl ether. After extractive work-up, 657 mg (1.60 mmol, 94%) of the title compound Ia 'were obtained as a pale yellow oil.
  • Example 1 82.4 mg (2.06 mmol, 2.0 eq, 60% in paraffin oil) of sodium hydride and 331 mg (1.03 mmol, 1 .0 eq) of selenodiphenol II were reacted with 244 ⁇ M (352 mg, 2.06 mmol, 2.0 eq) of benzyl bromide. After extractive work-up, 407 mg (0.810 mmol, 79%) of the title compound Ia "were obtained as a pale yellow oil.
  • benzyl bromide was added at 0 ° C., 19 ⁇ l (172 mg, 1 .01 mmol, 1.0 eq) and stirred at 0 ° C. for 30 minutes. After a further 16 hours at RT, the solvent was removed under reduced pressure.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne de nouveaux sélénodiphénols protégés sur au moins un groupe hydroxyle, ainsi que leurs procédés de production et leur utilisation comme ligand dans des complexes.
PCT/EP2016/054419 2015-11-25 2016-03-02 Sélénodiphénols protégés et leurs procédés de production WO2017088987A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206697A1 (de) * 2001-02-19 2002-08-29 Basf Ag Hydroformylierungsverfahren
DE102010043558A1 (de) * 2010-11-08 2012-05-10 Evonik Oxeno Gmbh Verfahren zur Hydroformylierung von ungesättigten Verbindungen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10206697A1 (de) * 2001-02-19 2002-08-29 Basf Ag Hydroformylierungsverfahren
DE102010043558A1 (de) * 2010-11-08 2012-05-10 Evonik Oxeno Gmbh Verfahren zur Hydroformylierung von ungesättigten Verbindungen

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
H. M. LIN ET AL.: "A novel and efficient synthesis of selenides", ARKIVOC, vol. VIII, 2012, pages 146 - 156
T. K. PAINE ET AL.: "Manganese complexes of mixed O, X, O-donor ligands (X = S or Se): synthesis, characterization and catalytic reactivity", DALTON TRANS., vol. 15, 2003, pages 3136 - 3144, XP055284786, DOI: doi:10.1039/B304765M
TAPAN KANTI PAINE ET AL: "Manganese complexes of mixed O, X, O-donor ligands (X = S or Se): synthesis, characterization and catalytic reactivity", DALTON TRANSACTIONS, no. 15, 1 January 2003 (2003-01-01), pages 3136 - 3144, XP055215909, ISSN: 1477-9226, DOI: 10.1039/b304765m *

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