WO1995006025A1 - Procede de preparation d'un acetal - Google Patents

Procede de preparation d'un acetal Download PDF

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Publication number
WO1995006025A1
WO1995006025A1 PCT/NL1994/000192 NL9400192W WO9506025A1 WO 1995006025 A1 WO1995006025 A1 WO 1995006025A1 NL 9400192 W NL9400192 W NL 9400192W WO 9506025 A1 WO9506025 A1 WO 9506025A1
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Prior art keywords
process according
group
ethylenically unsaturated
platinum
unsaturated organic
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PCT/NL1994/000192
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English (en)
Inventor
Onko Jan Gelling
Josephus Marie Hubertus Spronken
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Dsm N.V.
E.I. Du Pont De Nemours And Company
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Priority to AU77103/94A priority Critical patent/AU7710394A/en
Publication of WO1995006025A1 publication Critical patent/WO1995006025A1/fr

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    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to a process for the preparation of an acetal by hydroformylation of an ethylenically unsaturated organic compound, the ethylenically unsaturated organic compound being contacted with carbon monoxide, hydrogen, an alkanol and a metal- containing catalyst system.
  • a drawback of this known process is that the selectivity for acetals still needs to be improved.
  • the selectivity to terminal acetals is too low especially when starting from internal ethylenically unsaturated organic compounds.
  • the object of the present invention is a process for the preparation of acetals starting from an ethylenically unsaturated organic compound and yielding acetals, in particular terminal acetals, with high selectivity.
  • Terminal acetals are interesting compounds for the preparation of, for instance, terminal aldehydes and terminal alkanols.
  • the catalyst system comprises a) platinum or a platinum compound, b) a bidentate ligand with the general formula R 1 R 2 -M-R- M-R 3 R*, where M represents a phosphorus, antimony or arsenic atom, R represents a divalent bridging group having at least three atoms and where R 1 , R 2 , R 3 and R 4 represent the same or different hydrocarbon groups, which may or may not be substituted, c) and a Br ⁇ nsted acid with a pKa ⁇ 2 and/or a Lewis acid.
  • the catalyst system according to the invention is easier to recover from the reaction mixture than a volatile cobalt-based catalyst as described in, for instance, US-A-4209643.
  • the process according to the invention allows the products and the catalyst to be separated through simple distillation.
  • Terminal ethylenically unsaturated organic compounds as well as internal ethylenically unsaturated organic compounds may be converted with a high selectivity for terminal acetals.
  • Another advantage is that the use of tin chloride is not necessary to achieve the improved results. This is advantageous because tin chloride, generally used in Pt-catalysed hydroformylation as described in the literature, is very corrosive. It is known from US-A-2491915 that acetals may be prepared starting from ethylenically unsaturated organic compounds in the presence of carbon monoxide, hydrogen, alcohol and a Group VIII (or group 8, 9 and 10 of the new IUPAC notation) metal catalyst. Cobalt and ruthenium are referred to as being the most suitable Group VIII metal catalyst. However, the attained selectivity for acetals is low (around 70%).
  • EP-A-220767 discloses a catalyst consisting of platinum or a platinum compound, a bidentate phosphine ligand and an anion of a carboxylic acid with a pKa ⁇ 2, for hydroformylation of ethylenically unsaturated organic compounds to aldehydes.
  • Alkanols are not named as possible solvents and/or reagents and acetals are not named as possible products.
  • acids are applied instead of the anion of a carboxylic acid as in the above process.
  • alkanols as solvent is discouraged in the scientific literature for hydroformylation reactions that are catalyzed by platinum/tin systems (J. of Molecular Cat., 39 (1987) 180 and in J. Organometall Chem. 286 (1985), 115-120).
  • Acetals prepared according to the invention may be represented by the following general formula:
  • the source of R 7 and R 8 is the alkanol which is further described below.
  • the source of the R 5 -C-C-R 6 portion is the ethylenically unsaturated organic compound, which ethylenically unsaturated organic compound is further described herein below.
  • R 5 represents an H.
  • the ethylenically unsaturated organic compound will be an alkene or a cycloalkene containing from 3 to 30 carbon atoms and, if the ethylenically unsaturated organic compound is an internal ethylenically unsaturated organic compound, containing from 4 to 30 carbon atoms, preferably from 4 to 12 carbon atoms.
  • the ethylenically unsaturated organic compound may or may not be functionalized. Examples of functionalized organic compounds will be described below. Mixtures of ethylenically unsaturated organic compounds with different numbers of carbon atoms may also serve as starting material.
  • the ethylenically unsaturated organic compound may be a terminally ethylenically unsaturated organic compound.
  • Terminally ethylenically unsaturated organic compounds are very suitable because with the process according to the invention these compounds can be converted to terminal acetals with a high selectivity.
  • Internally ethylenically unsaturated organic compounds are also suitable starting compounds because the process according to the invention allows terminal acetals to be prepared with high selectivity.
  • Terminal acetals may also be prepared by the process according to the invention with high selectivity starting from mixtures of isomeric ethylenically unsaturated organic compounds (which differ in the location of the ethylenically unsaturated bond).
  • the ethylenically unsaturated organic compounds preferably are terminal, but the ethylenically unsaturated organic compounds may also be branched or cyclic.
  • Examples of such ethylenically unsaturated organic compounds are propylene, butene-1, butene-2, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-hexene, 3- hexene, 2-methyl-l-butene, 2-methyl-2-butene, 1-hexene, 3- methyl-1-pentene, 2-methyl-2-pentene-, 2-heptene, 2- methyl-2-hexene, 3-methyl-2-hexene, 1-octene, 4-octene, 2- octene, 3-methyl-l-heptene, 2-methyl-2-heptene, 3-nonene, 3-methyl-2-octene, 2-decene, 5-decene, 3,4-dimethyl-2- octene,
  • the ethylenically unsaturated organic compound may also be an ethylenically, optionally internally unsaturated alcohol, aldehyde, ketone, ester, carboxylic ester or nitrile having from 3 to 30 carbon atoms.
  • examples of such compounds are acrylic acid, methacrylic acid and the alkyl esters of these acids, wherein the alkyl group can contain 1 to 12 carbon atoms.
  • An especially suitable group of esters and acids is represented by the following chemical formula:
  • R 9 represents a monoethylenically unsaturated- or poly-ethylenically unsaturated acyclic hydrocarbon group having from 3 to 11 carbon atoms, which group may or may not be branched
  • R 10 represents a hydrogen group or an alkyl group having from 1 to 8 carbon atoms or an aryl group or an arylalkyl group having from 6 to 12 carbon atoms.
  • R 9 can be for example the radical groups of the afore mentioned non-functionalized ethylenically unsaturated organic compounds; especially propylenyl, isobutenyl, pentyl, hexenyl.
  • R 9 is preferably a linear butenyl group because the corresponding acetals may serve as, for example, starting material for the preparation of Nylon-6 and Nylon-6.6 precursors.
  • R 10 preferably is a hydrogen group or an alkyl group having from 1 to 8 carbon atoms or a phenyl group or benzyl group.
  • R 10 preferably is a hydrogen group or an alkyl group having from 1 to 8 carbon atoms or a phenyl group or benzyl group. Examples of such groups are the methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, cyclohexyl, benzyl or phenyl groups.
  • a mixture of isomeric alkyl pentenoates can be prepared by a process as described in US-A-3253018.
  • Such a mixture substantially containing the internally olefinically unsaturated alkyl-3-pentenoate may with advantage be converted to the corresponding terminal dialkylacetal by means of the process according to the invention.
  • alkanols that are suitable for the process according to the invention are liquid, low- molecular weight alkanols.
  • the alkanols may be primary or secondary alkanols. Suitable alkanols are 2-dodecanol, isopropanol, cyclohexanol and 2,2-dimethyl propanol.
  • Monohydric alkanols having from 1 to 5 carbon atoms are preferred.
  • alkanols are ethanol, ethanol, propanol, isopropanol, n-pentanol, 2- methylpropanol and n-butanol.
  • Methanol is applied with the most preference.
  • the molar ratio of ethylenically unsaturated organic compound and alkanol is between 1:1000 and 1:3, preferably between 1:100 and 1:5.
  • Platinum or the platinum compound may be applied in a homogeneous system or an immobilized heterogeneous system. Preferably, homogeneous systems are applied. Since platinum reacts with the bidentate ligand in situ to form a complex, the choice of initial Pt compound is not in general critical. Suitable platinum compounds are salts of platinum with, for example, hydrohalogenic acids, nitric acid, sulphonic acid and carboxylic acids having not more than 12 carbon atoms per molecule.
  • Platinum halides such as PtCl 2 and CODPtCl 2 are preferably applied as platinum compounds since these compounds are also Lewis acids. Application of such platinum halides obviates the need to add an extra Lewis acid to the reaction mixture. Platinum chloride compounds are applied with the most preference.
  • the molar ratio between platinum and ethylenically unsaturated organic compound lies between 1:1 and 1:1000. Higher ethylenically unsaturated organic compound/Pt ratios are less favourable in that the reaction will proceed more slowly.
  • the lower limit is not critical but for practical reasons the ratio will not be chosen on the low side. Consequently, the molar ratio between platinum and ethylenically unsaturated organic compound preferably lies between 1:50 and 1:300.
  • Suitable Br ⁇ nsted acids are acids with pKa ⁇ 2 (measured in an aqueous solution at 18°C).
  • suitable inorganic acids are sulphonic acids, phosphoric acid and hydrogen halides for example HC1 and HBr.
  • suitable carboxylic acids are trichloroacetic acid, trifluoroacetic acid, dichloroacetic acids, difluoroacetic acid. Fluorinated alkyl-carboxylic acids and, in particular, trifluoroacetic acid are preferably used as Br ⁇ nsted acid.
  • the Br ⁇ nsted acid content of the reaction mixture is higher than 1, particularly higher than 3 equivalents of acid per mole of platinum.
  • the Br ⁇ nsted acid content generally is lower than 50, particularly lower than 10 and most preferably lower than 5 equivalents of acid per mole of platinum.
  • Suitable Lewis acids are, for example, metal halides.
  • the metal halide will react to form a hydrogen halide compound when dissolved in the alkanol according to the invention.
  • suitable tin halides are SnCl 2 , SnBr 2 , Snl 2 , Sn(BF 4 ) 4 , SnCl 4 and SnCl 2 .2H 2 0.
  • Platinum halides and SnCl 2 are preferably applied.
  • the molar ratio between metal halide compound and platinum lies between 0.1:1 and 1000:1, preferably between 1:1 and 20:1.
  • R X R 2 -M-R-M-R 3 R 4 preferably is a bidentate phosphine, where M represents a phosphorus atom.
  • the bridging group R can be a divalent organic bridging group having at least 3 carbon atoms in the bridge or a divalent organometallic bridging group.
  • Preferred organic bridging groups -R- can be represented by the following general chemical formula:
  • R 11 and R 12 can be hydrogen or hydrocarbon groups with 1 to 10 carbon atoms and in which n is between 3 and 10 .
  • R 11 and R 12 are hydrocarbon groups which offer a steric hindrance. Because of this steric hindrance the R I R 2 -M- and -M-R 3 R 4 will not be able to freely rotate relative to each other compared to the situation in which a less sterically hindred bridge is used.
  • the term "rigid group” shall also be defined for the purposes of the present invention as a group having "limited flexibility” or a group having "at least a partially rigid link", as is known to one of ordinary skill in the art.
  • the shortest distance between the two M's for the organic bridging group is preferably a chain of 4 atoms; besides carbon, the atoms may represent a heteroatom such as nitrogen, oxygen, sulphur and phosphorus.
  • Suitable "rigid" bridging groups are bivalent organic groups containing at least one divalent cyclic group, which may or may not be aromatic. This cyclic group imparts the rigid properties to the bridging group and is linked to M whether or not via an alkyl group having from 1 to 3 carbon atoms.
  • a suitable group of bridging groups may be represented by the following general formula:
  • Y represents a divalent organic group, which group contains at least one divalent cyclic structure as a rigid link (which cyclic structure imparts the rigidity to the bridging group), the cyclic structure optionally being substituted and which organic group Y may contain heteroatoms such as oxygen, nitrogen, phosphorus and sulphur, and where R 13 and R 14 may independently of one another be omitted or independently of one another represent a C 1 -C 3 alkylene group. R 13 and R 14 are preferably omitted or are methylene groups or are substituted with other groups in order to increase the rigidity of the bridging group. As a rule, the cyclic structure will contain from 3 to 20 atoms.
  • An example of a bidentate phosphine with a cyclic structure in Y containing a heteroatom is the commercially obtainable 2,3-0-isopropylidene-2,3- dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP).
  • DIOP 2,3-0-isopropylidene-2,3- dihydroxy-1,4-bis(diphenylphosphino)butane
  • cyclic alkanes such as cyclopropane, cyclobutane, cyclopentane and cyclohexane.
  • Bridged cycloalkanes are highly suitable as cyclic structure of Y. Examples of such bridged cycloalkanes are bicyclofl,l,2]hexane, bicyclo[2,2,l]heptane and bicyclo[2,2,2]octane.
  • the cyclic structure of Y may optionally be substituted with one or more aryl groups or alkyl groups or other groups. These groups may optionally be used for immobilizing the bidentate phosphine onto a carrier. Examples of such groups are, for instance, carboxyl groups, hydroxyl groups, amino groups and halide groups.
  • Possible divalent organometallic bridging groups are bis( -cyclopentadienyl) coordination compounds of metals (also known as metallocenes) . Possible metals are Fe, Zr, Co, Cr, Ni, Ti, Ru and W. A particularly suitable metallocene is the ferrocenyl group (Fe). It seems that the organometallic bridging groups act as having a rigid link.
  • R 1 , R 2 , R 3 , and R 4 may be C 1 -C 15 (cyclo)alkyl groups or C 5 -C 20 aryl groups.
  • (cyclo)alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, tert.butyl, pentyl, cyclohexyl, and cyclooctyl groups. These groups preferably are aryl groups such as naphthyl, phenyl or a heterocyclic aryl group such as pyridyl. These aryl groups may optionally be substituted.
  • substituents are alkyl groups such as a methyl, ethyl and iso-butyl group, alkoxy groups, halides and amine derivatives.
  • bidentate phosphines are 2,3-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphos- phino)butane (DIOP) (A), bis(diphenylphosphine)ferrocene (B) , trans-l,2-bis(di(m-methylphenyl)phosphinomethyl)- cyclobutane (C), trans-[ (bicyclo[2.2.l]heptane-2,3- diyl)bis(methylene) ]-bis[ iphenylphosphine] (D) , trans- [ (bicyclo[2.2.2]octane-2,3-diyl)bis(methylene) ]- bis[diphenylphosphine] (E), trans-1,2-bis(diphenyl- phosphinomethyl)cyclobutane (DPMCB) (F) and trans-1,2- bis[diphenylphosphinomethyl]
  • the molar ratio between platinum and bidentate ligand as a rule lies between 1:2 and 2:1. Most preferably, this ratio is about 1:1.
  • the temperature at which the process according to the invention is carried out lies between 20 and 180°C.
  • the temperature will more particularly lie between 80 and 140°C and, if the ethylenically unsaturated organic compound is a pentenoate, the temperature will preferably lie between 90 and 110°C.
  • the pressure as a rule lies between 2 and 60 MPa. More unwanted hydrogenation will occur at pressures below 2 MPa whilst the reaction will proceed less rapidly at pressures higher than 60 MPa.
  • the reaction preferably is effected at a pressure which lies between 6 and 15 MPa.
  • the molar ratio between hydrogen and carbon monoxide as a rule lies between 10 : 1 and 1 : 10. Preferably, this ratio lies between about 3 : 1 and 1 : 5.
  • Any aldehyde formed during the reaction may readily be converted to the acetal using techniques known to one skilled in the art. Examples of such techniques are cited in US-A-2842576.
  • the acetal that has formed may readily be separated off from the reaction mixture through distillation at reduced pressure.
  • the invention is also directed to a process for the preparation of an aldehyde by hydrolysis of the acetal prepared by the above described process.
  • the acetal may readily be converted to the corresponding aldehyde through commonly known techniques such as hydrolysis with a dilute mineral acid.
  • More in particular is the invention also directed to a process to prepare alkyl 5- formylvalerate starting from alkyl 3-pentenoate by hydrolysis of the alkyl 5-formylvalerate dialkylacetal (see above for the scope of the alkyl 3-pentenoate) .
  • This process is advantageous because it is possible to prepare alkyl 5-formylvalerate when starting from alkyl 3- pentenoate with a higher selectivity and at lower pressure than the known state of the art processes as for example described in EP-A-295549.
  • the acetal conversion to the aldehyde is generally performed at a temperature between 0 and 80°C and preferably between 10 and 60°C.
  • the reaction can be performed in vacuo or under pressure.
  • the reaction can be performed in the absence of an additional solvent or in the presence of a solvent which is inert under reaction conditions.
  • Preferably water, which is needed for the hydrolysis can be used as a solvent in a molar ratio of water:acetal of between 5:1 and 100:1.
  • the hydrolysis is usually carried out in the presence of an acid catalyst.
  • homogeneous acids are sulfuric acid, phosphoric acid, hydrochloric acid, or any other mineral acid.
  • heterogeneous acids are used because they can be more easily separated from the reaction mixture.
  • heterogeneous acid catalysts are ion exchange resins and zeolites. Examples of suitable ion exchange resins are Duolite® C 265, Lewasorb® AC 10, Lewatit® SPC 118 and Amberlyst® 15.
  • the aldehyde prepared by the above described process can easily be separated from an aqueous reaction mixture by distillation or by extraction with a solvent which is not miscible with water.
  • suitable solvents are methylchloride, chloroform, toluene, benzene, methyl tert-butylether, diethylether, ethylacetate or any other commonly used organic extraction solvent. Further purification of the aldehyde can be performed by distillation.
  • the acetal can also be used as a starting compound for the preparation of an amino compound by reductive amination of the acetal group in the presence of ammonia, hydrogen and a hydrogenation catalyst and optionally a solvent.
  • the invention is in particular also directed to a process for the preparation of 6- aminocaproate by reductive amination of the corresponding 5-formylvalerate dimethylacetal prepared by the above described process.
  • the reductive amination can be performed in any manner known to the man skilled in the art. JP-A-25351/1966 for example describes a suitable process for the reductive amination.
  • solvent for the reductive amination the alkanol used for the preparation of the acetal can be advantageously used. This is for example advantageous because the alkanol does not have to be separated from the acetal before the reductive amination.
  • the acetal may also be converted to the corresponding alkanol.
  • DE-A-2357645 discloses a process for the preparation of an alkanol starting from an acetal in the presence of carbon monoxide, hydrogen, rhodium and a tertiary amine. Terminal alkanols may well be used as surfactants or as plasticizers.
  • the invention is elucidated by means of the following non-limiting examples.
  • MeOH methanol
  • Example 1 was repeated using 4-octene in place of 2-octene.
  • the mixture was analyzed after a reaction time of 4 hours.
  • the conversion was 18% with a selectivity for dimethyl acetals of 95% and a selectivity for the terminal 1,1-dimethoxynonane of 73%.
  • N/Br ratio between terminal acetals and branched acetals
  • Example III was repeated using different bidentate phosphine ligands.
  • the results are stated in Table 3.
  • the letters refer to the compounds in the sheet of formulae.
  • Pt(AcAc) 2 was used in place of CODPtBF 4 AcAc as Pt compound.
  • Example III was repeated.
  • the methyl-5- formylvalerate dimethylacetal was isolated by distillation and a solution of 10 g methyl-5-formylvalerate dimethylacetal, 50 g water and 1 g of Amberlyst® 15 was mixed for 1 hour at 40°C. After separating the catalyst by filtration the resulting reaction mixture was analysed: the conversion of methyl-5-formylvalerate dimethylacetal was 93% and the selectivity to the methyl 5-formylvalerate was 96%.
  • CO/H 2 1/1 mol/mol
  • catalyst system comprises: 0 a) platinum or a platinum compound, b) a bidentate ligand with the general formula R X R 2 - M-R-M-R 3 R 4 , where M represents a phosphorus, antimony or arsenic atom, R represents a divalent bridging group having at least three 5 atoms, and where R 1 , R 2 , R 3 and R 4 represent the same or different hydrocarbon groups, whether or not substituted, c) and a Br ⁇ nsted acid with a pKa ⁇ 2 and/or a Lewis acid.
  • Process according to Claim 5 characterized in that the molar ratio between platinum and bidentate ligand is about 1:1. 5 7. Process according to any one of Claims 1-6 characterized in that the ratio between Br ⁇ nsted-acid equivalents and platinum lies between 0.1:1 and 1000:1 (eq:mol).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de préparation d'un acétal par hydroformylation d'un composé organique éthyléniquement insaturé. On met en contact le composé organique éthyléniquement insaturé et du monoxyde de carbone, de l'hydrogène, un alcanol et un système catalyseur renfermant un métal. Ledit système catalyseur comporte (a) du platine ou un composé platiné; (b) un ligand bidenté répondant à la formule générale R1R2-M-R-M-R3R4, dans laquelle M représente un atome de phosphore, d'antimoine ou d'arsenic, R représente un groupe bivalent de pontage possédant au moins trois atomes, et R?1, R2, R3 et R4¿ représentent les mêmes groupes hydrocarburés éventuellement substitués ou des groupes hydrocarburés éventuellement substitués différents; et (c) un acide de Brönsted ayant un pKa inférieur à 2, et/ou un acide de Lewis.
PCT/NL1994/000192 1993-08-23 1994-08-15 Procede de preparation d'un acetal WO1995006025A1 (fr)

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AU77103/94A AU7710394A (en) 1993-08-23 1994-08-15 Process for the preparation of an acetal

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BE9300860 1993-08-23
BE9300860A BE1007410A3 (nl) 1993-08-23 1993-08-23 Werkwijze voor de bereiding van een acetaal.

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US5710337A (en) * 1995-05-30 1998-01-20 Hoechst Celanese Corporation Synthesis of and hydroformylation with fluoro-substituted bidentate phosphine ligands
US5886236A (en) * 1997-04-15 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acid salts
EP0918781A1 (fr) * 1996-06-14 1999-06-02 The Penn State Research Foundation Synthese asymetrique catalysee par des complexes de metaux de transition avec des ligands chiraux cycliques
US5925754A (en) * 1997-04-15 1999-07-20 Union Carbide Chemicals & Plastics Technology Corporation Epsilon caprolactam compositions
US5936127A (en) * 1997-01-13 1999-08-10 The Penn State Research Foundation Asymmetric synthesis and catalysis with chiral heterocyclic compounds
US5962680A (en) * 1997-04-15 1999-10-05 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing epsilon caprolactams
US6207868B1 (en) 1997-06-13 2001-03-27 The Penn State Research Foundation Asymmetric synthesis catalyzed by transition metal complexes with chiral ligands
WO2001046119A1 (fr) * 1999-12-20 2001-06-28 General Electric Company Composition catalytique et procede de production de carbonates diaryliques au moyen de diphosphines
US6399787B1 (en) 1997-06-13 2002-06-04 Penn State Research Foundation Catalytic asymmetric hydrogenation, hydroformylation, and hydrovinylation via transition metal catalysts with phosphines and phosphites
US6951833B2 (en) 2002-09-17 2005-10-04 O'neil Deborah Anti-microbial compositions
RU2540079C2 (ru) * 2013-03-06 2015-01-27 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Дифосфины, катализатор синтеза сложных эфиров на их основе и способ синтеза сложных эфиров в его присутствии
CN115850328A (zh) * 2021-09-23 2023-03-28 南开大学 环丙烷骨架双膦配体与其钴配合物和制备方法及应用

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US2533276A (en) * 1949-07-26 1950-12-12 Rohm & Haas Preparation of ester-acetals
US4209643A (en) * 1978-12-11 1980-06-24 Ethyl Corporation Preparation of acetals
EP0094748A1 (fr) * 1982-05-11 1983-11-23 Imperial Chemical Industries Plc Procédé de production de monoaldéhydes saturés et dialdéhydes non saturés et leurs acétales
EP0220767A1 (fr) * 1985-10-29 1987-05-06 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'aldéhydes
WO1988008835A1 (fr) * 1987-05-14 1988-11-17 Colorado State University Research Foundation Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres

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US2491915A (en) * 1946-06-07 1949-12-20 Du Pont Process for the preparation of acetals
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EP0094748A1 (fr) * 1982-05-11 1983-11-23 Imperial Chemical Industries Plc Procédé de production de monoaldéhydes saturés et dialdéhydes non saturés et leurs acétales
EP0220767A1 (fr) * 1985-10-29 1987-05-06 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'aldéhydes
WO1988008835A1 (fr) * 1987-05-14 1988-11-17 Colorado State University Research Foundation Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres

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US5710337A (en) * 1995-05-30 1998-01-20 Hoechst Celanese Corporation Synthesis of and hydroformylation with fluoro-substituted bidentate phosphine ligands
EP0918781A1 (fr) * 1996-06-14 1999-06-02 The Penn State Research Foundation Synthese asymetrique catalysee par des complexes de metaux de transition avec des ligands chiraux cycliques
EP0918781A4 (fr) * 1996-06-14 1999-07-28 Penn State Res Found Synthese asymetrique catalysee par des complexes de metaux de transition avec des ligands chiraux cycliques
US6037500A (en) * 1996-06-14 2000-03-14 The Penn State Research Foundation Asymmetric synthesis catalyzed by transition metal complexes with cyclic chiral phosphine ligands
US5936127A (en) * 1997-01-13 1999-08-10 The Penn State Research Foundation Asymmetric synthesis and catalysis with chiral heterocyclic compounds
US5886236A (en) * 1997-04-15 1999-03-23 Union Carbide Chemicals & Plastics Technology Corporation Process for producing aldehyde acid salts
US5925754A (en) * 1997-04-15 1999-07-20 Union Carbide Chemicals & Plastics Technology Corporation Epsilon caprolactam compositions
US5962680A (en) * 1997-04-15 1999-10-05 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing epsilon caprolactams
US6207868B1 (en) 1997-06-13 2001-03-27 The Penn State Research Foundation Asymmetric synthesis catalyzed by transition metal complexes with chiral ligands
US6278024B1 (en) 1997-06-13 2001-08-21 The Penn State Research Foundation Asymmetric synthesis catalyzed by transition metal complexes with rigid chiral ligands
US6380416B2 (en) 1997-06-13 2002-04-30 The Penn State Research Foundation Asymmetric synthesis catalyzed by transition metal complexes with rigid chiral ligands
US6399787B1 (en) 1997-06-13 2002-06-04 Penn State Research Foundation Catalytic asymmetric hydrogenation, hydroformylation, and hydrovinylation via transition metal catalysts with phosphines and phosphites
WO2001046119A1 (fr) * 1999-12-20 2001-06-28 General Electric Company Composition catalytique et procede de production de carbonates diaryliques au moyen de diphosphines
US6407027B2 (en) 1999-12-20 2002-06-18 General Electric Company Catalyst composition and method for producing diaryl carbonates, using bisphosphines
US6951833B2 (en) 2002-09-17 2005-10-04 O'neil Deborah Anti-microbial compositions
RU2540079C2 (ru) * 2013-03-06 2015-01-27 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Дифосфины, катализатор синтеза сложных эфиров на их основе и способ синтеза сложных эфиров в его присутствии
CN115850328A (zh) * 2021-09-23 2023-03-28 南开大学 环丙烷骨架双膦配体与其钴配合物和制备方法及应用

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