RU2038844C1 - Catalytic composition for ethylene oxide hydroformylation, method of its preparing and a method of synthesis of 1,3-propanediol and 3-hydroxypropionic aldehyde - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: 1,3-propanediol and 3-hydroxypropionic aldehyde. Reagent 1: ethylene oxide. Reagent 2: carbon monoxide and hydrogen. Reaction conditions: catalytic composition containing anionic rhodium-containing complex with phosphite ligand at molar ratio ligand to rhodium 0.1-100; ionic component linked with noncovalent bonds with anionic rhodium-containing component at molar ratio of ionic component to rhodium 0.1-10, and cation distinct from hydrogen ion, at molar ratio of cation to rhodium 0.1-100. Composition is used in organic synthesis. EFFECT: improved properties of composition. 16 cl

Description

 The invention relates to the production of 1,3-diols and / or 3-hydroxyaldehydes from epoxides. The invention relates to hydroformylation catalysts, a method of manufacturing hydroformylation catalysts, and to methods using hydroformylation catalysts to produce such 1,3-diols and / or 3-hydroxyaldehydes from epoxides.

 Glycols are usually valuable chemical compounds that find a variety of uses. Such compounds are used, for example, as intermediate chemical products in the production of esters, as well as in the synthesis of polyesters. In particular, 1,3-propanediol has been found to be particularly useful in a number of applications. 1,3-propanediol was prepared by acid-catalyzed hydration of acrolein to form 3-hydroxypropanal, which was then hydrogenated to the corresponding diol. Due to the relatively low reaction rates and yields of the products obtained, this attempt did not lead to a viable process for the production of 1,3-propanediol in large commercial quantities.

 The preparation of 1,3-diols, for example 1,3-glycols, by hydroformylation of epoxides using phosphine-modified cobalt carbonyl complexes as a catalyst is described by Smith et al. US Pat. No. 3,463,819. In particular, this patent shows the production of 1,3-propanediol by hydroformylation of ethylene oxide using a tertiary phosphine-modified catalyst from cobalt carbonyl. To ensure good yields of 1,3-propanediol, very high concentrations of cobalt-containing catalyst are required.

 Lawrence et al. US Pat. No. 3,687,981 describes a process for producing 1,3-propanediol, which employs two separate steps. In a first step, ethylene oxide is subjected to a hydroformylation reaction in the presence of a hydroformylation catalyst containing a transition metal, especially a Group VIII metal of the Periodic System, for example carbonyl cobalt-tertiary phosphine and carbonyl rhodium, to give 2- (2-hydroxyethyl) -4-hydroxy-1,3- dioxane. The dioxane compound, together with a small amount of 3-hydroxyproionaldehyde, is separated from the hydroformylation solvent and catalytically hydrogenated to produce 1,3-propanediol.

 Smith et al. US Pat. No. 3,456,017 describes the preparation of 1,3-propanediol by hydroformylation of ethylene oxide using a dicobalt hexacarbonyl complex as a catalyst in which the two remaining coordination centers of cobalt fragments are complexed to one or more tertiary phosphine ligands.

 Horvits et al. US Pat. No. 4,323,355 describes the reaction of an olefin with an aldehyde in the presence of a strong acid catalyst and cocatalyst selected from antimony and bismuth oxides and their salts to produce one or a mixture of 1,3-difunctional compounds.

 European Patent Application No. 0257967 describes a method for producing 1,3-glycols by reacting an epoxide with synthesis gas in an acidic medium in the presence of rhodium and phosphine. A reaction mixture containing epoxide, rhodium, phosphine, water, carbon monoxide, hydrogen and acid is described. A wide range of molar ratios of acid to rhodium is described, for example, from 10/1 to 1/10, this publication discloses the preferred molar ratio of acid to rhodium of about 1. An induction period of about 0.5-1 hours or more takes place after the formation of the reaction mixture before gas supply. Such an “induction period”, which in itself is detrimental because it requires a larger reactor volume and / or a longer time to obtain a given amount of 1,3-diol, is partly the result of combining a certain amount of epoxide with rhodium and phosphine and possibly other components to obtain a true hydroformylation catalyst. Therefore, a certain amount of epoxide is included in the hydroformylation catalyst. The use of epoxide to obtain a catalyst reduces the maximum yield of the desired products, for example 1,3-diol. Obviously, a rhodium-containing catalyst that does not require an induction period and / or which is made without the inclusion of an epoxide is more advantageous.

 Marphy et al. US Pat. No. 4,873,378 describes essentially the same process as described in the aforementioned European patent publication. In addition, it is described that a salt having an alkali metal cation and a solubilizing anion is also present in the reaction mixture. This patent describes that the “induction period” is eliminated in some examples containing relatively large amounts of alkali metal salts.

 Marphy et al. US Pat. No. 4,873,379 describes a process for preparing 1,3-diols. This patent describes a reaction mixture containing epoxide, rhodium, a promoting alkali metal salt, water, carbon monoxide and hydrogen. No other promoter is proposed than alkali metal salts.

 Mayer et al. US Pat. No. 4,774,361 describes a solubilized rhodium phosphite complex catalyzing a liquid hydroformylation process with a recycle to produce an aldehyde by reacting an olefinic unsaturated compound with carbon monoxide and hydrogen. Billig et al. US Pat. Nos. 4,668,651 and 4,769,498 describe a complex catalyst of a Group VIII transition metal with a polyphosphite ligand and a free polyphosphite ligand to produce aldehydes in which the olefin compound reacts with carbon monoxide and hydrogen. Billig et al. US Pat. No. 4,885,401 describes the hydroformylation of olefinically unsaturated organic compounds with carbon monoxide and hydrogen in the presence of a rhodium catalyst complexed to a bisphosphite ligand. Billig et al. US Pat. Nos. 4,717,775 and 4,599,206 describe the hydroformylation of an olefinically unsaturated organic compound with carbon monoxide and hydrogen in the presence of a rhodium-containing catalyst complexed to a diorganophosphite ligand.

In the article "Aspects of the action of anionic complexing rhodium ligands" A.S. Chan et al. Journal of Oranometallic chemictry 279 (1985), 171-179, shows some anionic rhodium complexes that have been studied as formaldehyde hydroformylation catalysts. Various crystalline materials containing alkali metals were isolated, such as [Na / C ₁₂ H ₂₄ O ₆ ] [Rh (CO) ₃ (PRh ₃ )] and [K (C ₁₂ H ₂₄ O ₆ ) (Rh (CO) ₂ / P (ORh ₃ ) ₂ ]
Hydroformylation of epoxides has not been proposed.

 European Patent Publication No. 0306094 describes a process for hydroformylating certain acrylic acid derivatives in the presence of a homogeneous catalyst system consisting of a rhodium compound and one or more triphenylphosphites. Hydroformylation of epoxides has not been proposed.

 There remains a need for a new catalyst for hydroformylation of epoxides and a method for its manufacture and use, as, for the production of 1,3-diol and / or 3-hydroxyaldehydes.

 A new method for hydroformylating epoxides, a catalyst for use in such a method, and a method for producing such catalysts are described. The epoxide hydroformylation process provides high final yields of the desired products, such as 1,3-diols and / or 3-hydroxyaldehydes. The present catalytic hydroformylation process provides high reaction rates and high selectivity to the desired product or products. Advantageously, less stringent hydroformylation reaction conditions and / or lower catalyst concentrations can be used. In addition, the induction period, which was characteristic of some of the previously proposed processes for hydroformylation of epoxides, can be reduced in length or even eliminated in the present invention. In addition, the inclusion of one or more specific promoting components provides improved results. The present catalyst compositions and the hydroformylation process provide significant advantages, for example, provide cost-effectiveness and efficiency in the production of 1,3-diols and / or 3-hydroxyaldehydes.

 The present invention relates to a method for producing 1,3-diol and / or 3-hydroxyaldehyde. This process involves contacting a mixture of epoxide, carbon monoxide and hydrogen in the presence of a rhodium-containing catalyst composition effective to promote hydroformylation of epoxides under effective conditions to form 1,3-diol and / or 3-hydroxyaldehyde. The rhodium-containing catalyst composition comprises an anionic rhodium-containing complex and an electrophile. If present, the 3-hydroxyaldehyde product is preferably contacted with hydrogen under conditions effective to form the desired 1,3-diol.

The contacting of the epoxide occurs preferably in the presence of H ⁺ ions in an amount effective to facilitate hydroformylation of the epoxides. The anionic rhodium-containing complex preferably includes a phosphine-containing ligand, more preferably a phosphorus-oxygen-containing ligand, in particular at least one phosphite ligand. In one useful embodiment, the catalytic composition comprises a different cation than H ⁺ , and preferably a different cation than an alkali metal, in particular an organ-containing cation. The promoter component is preferably included to increase the hydroformylation rate of the epoxide and / or selectivity to 1,3-diol and / or 3-hydroxyaldehyde.

Another broad aspect of the invention includes a composition which consists of a liquid medium, an anionic rhodium-containing complex comprising a ligand containing phosphorus and oxygen; H ⁺ , other than covalently bonded to the complex, and a cation, other than H ⁺ . This composition has catalytic activity for promoting hydroformylation of epoxide. The promoter component is preferably included and is effective for increasing the rate and / or selectivity of the epoxide hydroformylation reaction.

In addition, another composition useful as an epoxide hydroformylation catalyst is provided. This composition includes a liquid medium, a rhodium-containing complex comprising a ligand containing phosphorus and oxygen; an ionic component having sufficient basicity to create an anionic complex and comprising a cation other than H ⁺ and H ⁺ . The composition has a catalytic activity promoting the hydroformylation of epoxides. The promoter component is preferably incorporated and is effective for increasing the rate and / or selectivity of the hydroformylation reaction of epoxides.

 The present invention relates to a method for producing rhodium-containing compositions, for example, catalytic compositions for hydroformylation of epoxides. This process consists in contacting, preferably in a liquid medium, a source of rhodium, a source of ligand and an ionic component, preferably an ionic component including an organo-cation, and preferably an acid under conditions effective to produce an anionic rhodium-containing complex including a ligand containing phosphorus and oxygen. This rhodium-containing composition, in particular the anionic rhodium-containing complex, has the activity of promoting hydroformylation of epoxides.

 The method of the present invention provides a process for producing 1,3-diols or 3-hydroxyaldehydes, which are precursors of 1,3-diols, by hydroformylation of epoxides. The desired 1,3-diols and 3-hydroxyaldehydes in their monomeric form contain one carbon atom and one oxygen atom more than an epoxide. So, for example, when the reactive epoxide is ethylene oxide containing two carbon atoms and one oxygen atom, the obtained 1,3-diol is 1,3-propanediol and the obtained 3-hydroxyaldehyde is 3-hydroxypropionaldehyde, each of which contains 3 carbon atoms and two oxygen atom. As used here, the terms "1,3-diol" and "3-hydroxyaldehyde" refer not only to the monomeric form of these compounds, but also to oligomeric forms, for example, in which the degree of polymerization is up to about 10, in particular dimers, trimers and tetramers. Mixed oligomers of 1,3-diols and 3-hydroxyaldehydes are also possible and are included in the field of such terms.

C

C

где каждый R выбран среди водорода, одновалентных алифатических или ароматических групп, содержащих 1-12 атомов углерода, двухвалентных алифатических групп, содержащих 4-6 атомов углерода и связи с другим R, который является двухвалентным. Например, когда один R является двухвалентной насыщенной алифатической группой, имеющей 4 атома углерода и один R, соединенный с каждым из атомом углерода в приведенной выше формуле, является водородом, тогда эпоксид является циклогексеноксидом. Примеры конкретных эпоксидов, которые являются полезными в настоящем изобретении, включают этиленоксид, пропиленоксид, 1,2-эпоксиоктан, циклогексеноксид и стиролоксид. Эпоксид может присутствовать во время, особенно в начале стадии гидроформилирования настоящего изобретения в широко меняющихся количествах, например, в концентрациях в интервале от примерно 0,01 до примерно 95% предпочтительно примерно от 0,5 до примерно 75 мас. считая на общую массу реагентов, катализатора и жидкой среды, присутствующих в этой стадии.Suitable epoxides have the formula:

C

C

where each R is selected from hydrogen, monovalent aliphatic or aromatic groups containing 1-12 carbon atoms, divalent aliphatic groups containing 4-6 carbon atoms and bonds to another R, which is divalent. For example, when one R is a divalent saturated aliphatic group having 4 carbon atoms and one R connected to each of the carbon atom in the above formula is hydrogen, then the epoxide is cyclohexene oxide. Examples of specific epoxides that are useful in the present invention include ethylene oxide, propylene oxide, 1,2-epoxyoctane, cyclohexene oxide and styrene oxide. The epoxide may be present during, especially at the beginning of the hydroformylation step of the present invention in widely varying amounts, for example, in concentrations ranging from about 0.01 to about 95%, preferably from about 0.5 to about 75 wt. based on the total weight of the reagents, catalyst and liquid medium present in this stage.

The hydroformylation reaction is carried out in the presence of, for example, a suitable liquid medium, which is preferably a solvent for the epoxide and rhodium-containing catalyst composition. Suitable liquid media are aliphatic hydrocarbon components, aromatic hydrocarbon components, including benzene, toluene, xylenes, and the like. ethers, including high molecular weight ethers, polyethers, especially polyglycol ethers, and cyclic ethers, amides, sulfones, alcohols, ketones, esters and mixtures thereof. Particular esters of suitable liquid media include glyme (dimethoxyethane), diglyme, tetrahlim (tetraethylene glycol dimethyl ether), tetrahydrofuran and oils, such as those sold under the trade name Yukon ^R by Union Carbide Corporation, which is a mixed glycol polyethylene ethylene ether. The liquid medium preferably solubilizes the catalyst and epoxy reagent. A preferred liquid medium does not substantially react with any of the other components present during the hydroformylation reaction. In a polar liquid medium, many of the components of the present catalyst composition are often present as individual charged particles, for example, complexes, ions, and the like. In a nonpolar liquid medium, these components are often present as ion pairs. Such components are referred to here, regardless of the type of liquid medium used, as individual charged particles, it should be understood that one or more of these components may not be present as such, for example, may be present in an ion pair. For lower molecular weight epoxides, for example ethylene oxide, a liquid medium such as glyme, tetralim, tetrahydrofuran and the like is useful. and mixtures thereof. For higher molecular weight epoxides, petroleum ethers and hydrocarbon materials such as benzene, toluene and xylenes may be suitable.

 An important preferred feature of the present invention is the use of a liquid medium for hydroformylating epoxides, in particular low molecular weight epoxides, such as those containing 2-5 carbon atoms, especially ethylene oxide, in which the product 1,3-diol and / or 3-hydroxyaldehyde is insoluble or immiscible in a useful range of conditions. In particular, the present catalysts have significant activity and selectivity of 1,3-diols and / or 3-hydroxyaldehydes in the hydroformylation of low molecular weight epoxides using a liquid medium that was previously less suitable for such hydroformylation. Such a liquid medium, in particular hydrocarbons and mixtures thereof, especially aromatic hydrocarbons and mixtures thereof, are not only effective at the stage of hydroformylation of epoxides, but also form a two-phase mixture with the product 1,3-diol and / or 3-hydroxyaldehyde, in particular 3 -oxyaldehyde under these conditions, so that the product or products can be separated from the liquid medium, for example, using conventional phase separation techniques such as centrifugation, decantation, and the like.

So, in one embodiment, the present method for producing 1,3-diol and 3-hydroxyaldehyde comprises a step or steps in which the reaction mixture, after hydroformylation, in particular a liquid medium and a 3-hydroxyaldehyde product, causes the formation of a phase enriched in a liquid medium and phases enriched with 3-hydroxyaldehyde. In one particular useful embodiment, the reaction mixture is cooled from the temperature of the hydroformylation reaction to ensure the recovery of such phases. For example, cooling or maintaining the reaction mixture at a temperature ranging from about -50 ° C to ^about 50 ^C. In some cases, it causes the formation of the desired phases. Precautions should be taken to avoid temperatures at which a significant amount of liquid is cured. The phase enriched in a liquid medium has a higher concentration of the liquid medium and preferably a higher concentration of the components of the catalyst system than those in the total liquid reaction mixture and the 3-hydroxyaldehyde product after hydroformylation. Similarly, the 3-hydroxyaldehyde-enriched phase has a higher concentration of 3-hydroxyaldehyde than that found in the total or combined liquid reaction mixture and 3-hydroxyaldehyde product after hydroformylation.

 The liquid-enriched phase and the 3-hydroxyaldehyde-enriched phase that are in contact with each other are preferably separated, for example, using conventional phase separation techniques, to form the separated 3-hydroxyaldehyde material. This separated oxyaldehyde-enriched material, which includes a minor amount of other materials, such as a liquid medium and possibly 1,3-diol and other components present in the reaction mixture, is preferably then processed to obtain the desired 1,3-diol. The separated 3-hydroxyaldehyde-enriched material can be used directly in the hydrogenation step to produce 1,3-diol. This “direct” hydrogenation is especially useful when the liquid medium, including the 3-hydroxyaldehyde-rich material, is separated from hydrocarbons, in particular aromatic hydrocarbons such as benzene, toluene and xylenes. Such materials of the liquid medium essentially do not adversely affect the hydrogenation step. After hydrogenation, the resulting 1,3-diol can be separated, for example, using conventional techniques to obtain the desired 1,3-diol product of the desired purity. If desired, the material enriched in a liquid medium can be recycled for further use in the hydroformylation step.

The source of rhodium that is used to make the present catalyst composition may be in the form of metallic rhodium, rhodium salts and / or rhodium complexes. Among the sources of rhodium useful in the practice of the present invention, there are selected from one or more: metallic rhodium, rhodium oxides, RhI ₃ , RhBr ₃ , RhCl ₃ , Rh (acac) ₃ , Rh (CO) ₂ acac, Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , (RhCl (CO ₂ ) ₂ and Rh (NO ₃ ) ₃ , where acac means acetylacetonate. Rhodium can be used as a preformed anion, such as Rh ₆ (CO) ₁₅ ^2- and other similar anionic cluster rhodium salts.

 The concentration of rhodium in the hydroformylation reaction can be very dependent, for example, on the particular epoxide and the applied liquid medium and / or on the contacting conditions. Such a concentration is preferably in the range of from about 100 ppm (ppm) to about 10,000 ppm by weight, based on elemental rhodium, based on the total weight of the liquid medium and epoxide present during hydroformylation.

The term "complex", as used here and in the claims, means a coordination compound formed by combining one or more electron-enriched molecules or atoms capable of independent existence with one or more electron-depleted molecules or atoms, each of which also capable of independent existence. For example, the phosphite ligands used herein include at least one phosphorus donor atom having one available or lone pair of electrons and, therefore, capable of forming a coordination bond with rhodium. Carbon monoxide (which is also often classified as a ligand) is also present and forms a complex with rhodium. The finished composition of the anionic rhodium-containing complex may also contain an additional ligand, for example, hydrogen or anion filling the coordination centers or the nuclear charge of rhodium. Examples of additional ligands include, for example, halogen (Cl ^- , Br ^- , I ^- ), alkyl, aryl, substituted aryl, CF ₃ ^- , C ₂ F ₅ ^- , CN ^- , R ' ₃ PO and R'P (O) (OH) O), where each R 'is alkyl or aryl), acetate, acetylacetonate, SO ₄ ^2- , PF ₆ ^- , NO ₂ ^- , NO ₃ ^- , CH ₃ O ^- , CH ₂ = CHCH ₂ ^- , C ₆ N ₅ CN, CH ₃ CN, NO, NH ₃ , pyridine, monolefins, diolefins and triolefins, tetrahydrofuran and the like. Of course, it should be understood that the anionic rhodium-containing complex compounds preferably do not contain any additional organic ligands or anions that can poison the catalyst composition and have an undesirable detrimental effect on the performance of the catalyst composition. For example, it is known that when carrying out traditional hydroformylation reactions catalyzed by rhodium, halide anions and sulfur compounds can poison the catalyst. Therefore, it is preferred that the complexes are also free of halogen and sulfur directly bonded to rhodium, although this is not absolutely necessary.

 Therefore, the anionic rhodium-containing complexes in their simplest form preferably contain a certain amount of a ligand other than carbon monoxide, more preferably a phosphorus-containing ligand, and even more preferably a phosphorus and oxygen-containing ligand, in particular a phosphite ligand, and the amount of carbon monoxide is equal to two / 2 /, three / 3 / or four / 4 / moles in complex combination with one mole of rhodium. Therefore, the anionic rhodium-containing complex can be a complex mixture in monomeric, dimeric or higher forms of condensation, which are characterized by the presence of at least one ligand of the molecule, other than carbon monoxide, complexed with one rhodium atom. Carbon monoxide can and preferably also exists and is complexed with rhodium in the anionic rhodium-containing complex compound.

 An anionic rhodium-containing complex can be formed in advance, before introducing hydroformylation into the reaction zone, or an anionic rhodium-containing complex can be prepared in situ during hydroformylation. Such pre-formation or preparation preferably takes place in the presence of a free ligand other than carbon monoxide, although this may not be absolutely necessary.

 Any suitable ligand other than or additional to carbon monoxide can be used in the present anionic rhodium-containing complex. Of course, such a ligand should not have a noticeable deteriorating effect on the catalytic activity of the catalyst composition or on the hydroformylation of the epoxide as a whole. Phosphorus-containing ligands are preferred, phosphite ligands are more preferred.

Anionic rhodium-containing complexes preferably have significant stability under the conditions of the hydroformylation stage of epoxides. Thus, in one embodiment, the anionic rhodium-containing complex is preferably such that at least about 50% of the complex remains after 2 hours, more preferably after 5 hours, and even more preferably after 10 hours under conditions of hydroformylation of the epoxide, for example, under the indicated hydroformylation conditions epoxide. As used herein, the indicated epoxide hydroformylation conditions are as follows: Epoxide ethylene oxide Liquid glyme
Initial
mass ratio
epoxy to liquid 0.125 CO / H ₂ (molar) 1: 2 Pressure 1000 lb /
/ inch ²
(703 kg / cm ²⁾ Temperature 110 ^{° C} Rhodium concentration of 2000 hours / ml (wt.).

 Some materials, such as certain phosphines, have been found to be unstable under such conditions, for example, phosphonium ions are formed under such conditions from phosphine and available epoxide.

 As noted previously, it is more preferable when the ligands contain both oxygen and phosphorus. examples of such ligands include phosphonites, phosphinites and phosphites.

The phosphonites useful in the present invention preferably have the general formula
P (-OR ") ₂ (-CR"), while preferably useful in the present case, phosphinites have the general formula
P (-OR ") (- CR") ₂ , where each R "is independently selected from organic radicals, for example, hydrocarbon radicals and substituted hydrocarbon radicals, such as described elsewhere herein.

OX где R"' является двухвалентным органическим радикалом, а Х является одновалентным углеводородным радикалом, например, как более детально определено ниже.Examples of organophosphite ligands that can be used in the present invention include dorganophosphites having the formula
R

OX where R ″ is a divalent organic radical and X is a monovalent hydrocarbon radical, for example, as defined in more detail below.

 Typical divalent radicals represented by R ″ ″ are those in which R ″ ″ may be a divalent acyclic radical or a divalent aromatic radical. Typical divalent acyclic radicals include alkylene, alkylene-hydroxy-alkylene, alkylene-NX'-alkylene, where X 'is hydrogen or a monovalent hydrocarbon radical, alkylene-S-alkylene and cycloalkylene and the like. such as are more fully described, for example, in US patents NN 3415906 and 4567306, etc. descriptions of which are given here as a prior art. Typical divalent aromatic radicals include arylene, di-arylene, arylene-alkylene, arylene, alkylene-arylene, arylene-hydroxy-arylene, arylene-NX'-arylene and arylene-NX'-alkylene, where X 'is hydrogen or a monovalent hydrocarbon radical , arylene-S-alkylene and arylene-S-arylene and the like. More preferably, when R ″ is a divalent aromatic radical.

P O

X где каждая Ar группа является идентичной или различной, замещенной или незамещенной арильной группой; Х является одновалентным углеводородным радикалом, где m равно 1, и, когда m является другим, чем 1, m валентный радикал выбран в группе, состоящей из алкилена алкилен-окси-алкилена, арилена и арилен-(СН₂)_у-(Q)_n-CH₂)_y арилена, причем каждый ариленовый радикал является одинаковым или различным, замещенным или незамещенным ариленовым радикалом; каждый у индивидуально имеет величину Q или 1; каждый Q индивидуально является двухвалентной мостиковой группой, выбранной в группе, состоящей из -CR¹R²-, -O-, -S-, -NR^3-1, -S/R⁴P^5-1 и -СО-, где каждый радикал R¹ и R² индивидуально является радикалом, выбранным в группе, состоящей из водорода, алкила, содержащего 1-12 атомов углерода, фенила, толила, анизила, а каждый R³, R⁴ и R⁵ радикал индивидуально является водородом или метилом; каждый n индивидуально имеет величину 0 или 1, а имеет величину 1-6, предпочтительно 1-4. В одном варианте каждый у и каждый n имеют величину 0. Когда каждый n равен 1, соответствующий ему Q предпочтительно является мостиковой группой CR¹R², как определено выше, а более предпочтительно метиленом (-СН₂-) или алкилиденом (-CHR²-) c R², являющимся алкилом, содержащим 1-12 атомов углерода (например, метилом, этилом, пропилом, изопропилом, бутилом, изодецилом, додецилом и т.п. особенно метилом).Among the phosphite ligands used in the present invention, there are ligands of the general formula

PO

X wherein each Ar group is identical or different, substituted or unsubstituted aryl group; X is a monovalent hydrocarbon radical, where m is 1, and when m is other than 1, m is a valence radical selected in the group consisting of alkylene alkylene-hydroxy alkylene, arylene and arylene- (CH ₂ ) _y - (Q) _n -CH ₂ ) _y arylene, wherein each arylene radical is the same or different, substituted or unsubstituted arylene radical; each individual individually has a value of Q or 1; each Q is individually a divalent bridging group selected in the group consisting of -CR ¹ R ² -, -O-, -S-, -NR ^3-1 , -S / R ⁴ P ^5-1 and -CO-, where each radical R ¹ and R ^{2 is} individually a radical selected in the group consisting of hydrogen, alkyl containing 1-12 carbon atoms, phenyl, tolyl, anisyl, and each R ³ , R ⁴ and R ⁵ radical is individually hydrogen or methyl ; each n individually has a value of 0 or 1, and has a value of 1-6, preferably 1-4. In one embodiment, each y and each n have a value of 0. When each n is 1, the corresponding Q is preferably a CR ¹ R ² bridging group as defined above, and more preferably methylene (—CH ₂ -) or alkylidene (—CHR ² -) with R ² being alkyl containing 1-12 carbon atoms (e.g. methyl, ethyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc. especially methyl).

 Typical examples of monovalent hydrocarbon radicals represented by X when m is 1 in the above formula include substituted or unsubstituted monovalent hydrocarbon radicals containing 1-30 carbon atoms selected in the group consisting of substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl and alicyclic radicals. When m is 1, X is preferably a substituted or unsubstituted or unsubstituted radical selected in the group consisting of alkyl and aryl radicals.

 More specific typical monovalent hydrocarbon radicals represented by X include primary, secondary, and tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert.-butyl, tert.-butyl ethyl, tert. -butylpropyl, n-hexyl, amyl, sec-amyl, tert. -amyl, iso-octyl, 2-ethylhexyl, decyl, octadecyl and the like. aryl radicals such as phenyl, naphthyl, anthracyl and the like. aralkyl radicals such as tolyl, xylyl and the like. and alicyclic radicals such as cyclopentyl, cyclohexyl, cyclooctyl, cyclohexylethyl and the like. Preferably, unsubstituted alkyl radicals may contain 1-18 carbon atoms, more preferably 1-10 carbon atoms, while unsubstituted aryl, alkaryl and alicyclic radicals preferably contain 6-18 carbon atoms.

Typical m-valent radicals represented by X when m is other than 1 in the above formula include substituted and unsubstituted radicals selected in the group consisting of alkylene, alkylene-hydroxy-alkylene, phenylene, naphthylene, phenylene- (CH ₂ ) _for (Q) _m (CH ₂ ) -phenylene and naphthylene- (CH ₂ ) _y (Q) _m - (CH ₂ ) _y- naphthylene radicals, where Q, n and у have the meanings indicated above. More specific typical m-valent radicals represented by X when m is other than 1 are straight or branched chain alkylene radicals such as - (CH ₂ ) _x , where x has a value from 2 to about 18, preferably 2- 12, pentaerythritol, 1,2, 6-hexylene, etc. -CH ₂ CH ₂ OCH ₂ CH ₂ -, 1,4-phenylene, 2,3-phenylene, 1,3,5-phenylene, 1,3 -phenylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 1,1'- biphenyl-2,2'-diyl, 2,2'-biphenyl-1,1'-diyl, 1,1'-biphenyl-4,4-diyl, 1,1-binaphthyl-2,2-diyl, 2, 2-binaphthyl-1,1-diyl, phenylene-CH ₂ -phenyl, phenyl -S-phenylene, CH ₂ -phenyl-CH _2, phenylene-CH _(CH3) -phenyl, etc.

So, when m is other than 1, X is an m-valent radical which may contain 2-30 carbon atoms, moreover, alkylene and alkylene-oxy-alkylene radicals preferably contain 2-18 carbon atoms, and more preferably 2-12 atoms carbon, while radicals of the arylene type may contain 6-18 carbon atoms. In this embodiment, X is preferably an ethylene or arylene type radical, and more preferably a naphthylene or substituted or unsubstituted phenylene- (Q) _n phenylene radical.

Typical aryl radicals represented by Ar groups and arylene radicals X in the above formula include both substituted and unsubstituted aryl radicals. Such aryl radicals preferably contain 6-18 carbon atoms such as phenylene (C ₆ H ₄ ), naphthylene (C ₁₀ H ₆ ), anthracylene (C ₁₄ H ₈ ) and the like.

Typical substituted groups that may be present in the alkylene or arylene radicals X and the aryl groups represented by Ar in the above formula are monovalent hydrocarbon radicals such as substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or acyclic radicals, as well as silyl radicals such as —Si (R ⁶ ) ₃ and —Si (OR ⁶ ) ₃ , amino groups such as —N (R ⁶ ) ₂ , acyl radicals such as —C (O) R ⁶ , carbonyloxy radicals such as -C (O) R ^6, oxycarbonyl radicals such as -OC (O) R ^6, amido radicals such to to -C (O) N (R ⁶⁾ _2, and - (N) R ⁶ / C (O) _6, sulfonyl radicals such as -S- (O) ₂ R ^6, sulfinyl radicals such as -S (O ) R ⁶ , ethers (e.g. alkoxy) such as -OR ⁶ , thionyl ethers such as -SR ⁶ , phosphonyl radicals such as -P (O) (R ⁶ ) ₂ , and halogen, nitro, cyano trifluoromethyl and hydroxyl radicals, etc., where each R ⁶ individually means the same or different, substituted or unsubstituted monovalent radical, as defined here elsewhere, provided that in amine substituents such as —N (R ⁶ ) ₂ each R ^6, taken together, Mauger also represent a divalent bridging group that forms a heterocyclic radical with the nitrogen atom and in amino and amido substituents such as -N (R ⁶⁾ _2, -C (O) N (R ⁶⁾ ₂ and -N (R ⁶⁾ C (O) R ⁶ , each R ⁶ bonded to nitrogen may also be hydrogen, while in phosphonyl substituents such as —P (O) (R ⁶ ) ₂ , one R ⁶ may also be hydrogen. Preferably, the monovalent hydrocarbon substituent radicals, including those represented by R ⁶ , are unsubstituted alkyl or aryl radicals, although if desired, they, in turn, may be substituted with any substituent that does not undoubtedly adversely affect the process or composition of the present invention, such as, for example the hydrocarbon and non-hydrocarbon radicals indicated herein.

Among the more specific unsubstituted hydrocarbon substituent radicals, including those represented by R ⁶ that can be attached to the alkylene and / or arylene radicals of the X and / or Ar groups of the above formula that may be mentioned, are alkyl radicals, including primary, secondary and tertiary radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert.-butyl, neo-pentyl, n-hexyl, amyl, sec. amyl, tert. -amyl, iso-octyl, decyl and the like. aryl radicals such as phenyl, naphthyl and the like. aralkyl radicals such as benzyl, phenylethyl, triphenylmethyl and the like. and alicyclic radicals such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, cyclohexylethyl and the like. More specific non-hydrocarbon substituents that may be present in the alkylene and / or arylene radicals of X and / or Ar groups of the above formula are, for example, halogen, preferably chlorine or fluorine, —NO ₂ , —CN, —CF ₃ , —OH, -Si (CH ₃ ) ₃ , -Si (COH ₃ ) ₃ , -Si (C ₃ H ₇ ) ₃ , -C (O) CH ₃ , -C (O) C ₂ H ₅ , -OC (O) C ₆ H ₅ , -C (O) OCH ₃ , -N (CH ₃ ) ₂ , -NH ₂ , -NHCH ₃ , -NH (C ₂ H ₅ ), -CONH ₂ , -CON (CH ₃ ) ₂ , - S (O) ₂ C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅ , -OC ₆ H ₅ , -C (O) C ₆ H ₅ , -O (tert. -C ₄ H ₉ ), SC ₂ H ₅ , - (OCH ₂ CH ₂ ) ₃ OCH ₃ , - (OCH ₂ CH ₂ ) ₂ OCH ₃ , - (OCH ₂ CH ₂ ) OCH ₃ , -SCH ₃ , -S (O) CH ₃ , -SC ₆ H ₅ , -P (O) (C ₆ H ₅ ) ₂ , -P (O) (CH ₃ ) ₂ , -P (O) (C ₂ H ₅ ) ₂ , -P (O) (C ₃ H ₇ ) ₂ , P (O) (C ₄ H ₉ ) ₂ , -P (OO) (C ₆ H ₁₃ ) ₂ , -P (O) CH ₃ (C ₆ H ₅ ), -P (O) (H) (C ₆ H ₅ ), -NHC (O) CH ₃ and t n. Substituting radicals present in the alkylene and / or arylene radicals of X and / or Ar groups of the above formula may also contain 1-18 carbon atoms and may be attached to alkylene and / or arylene radicals of X and / or Ar groups in any suitable position, as they can be a linking group - (CH ₂ ) _y - (Q) _n - (CH ₂ ) _y - connecting two Ar groups or two arylene groups X in the above formula. In addition, each Ar radical and / or alkylene and / or arylene radical X may contain one or more substituent groups, these substituent groups may also be the same or different in any given phosphite. Preferred substituent radicals include alkyl and alkoxyl radicals containing 1-18 carbon atoms, and more preferably 1-10 carbon atoms, especially tert.-butyl and methoxy.

Among the more preferred phosphite ligands are those in which two Ar groups are connected by a bridge group represented by - (CH ₂ ) _y - (Q) _n - (CH ₂ ) _y in the above formula and are linked through their ortho-positions with respect to the atoms oxygen, which connect the Ar group to the phosphorus atom. It is also preferred that any substituent radical, when present in such Ar groups, is bound at the para- and / or ortho position of the aryl with respect to the oxygen atom that joins the substituted Ar group to the phosphorus atom.

P-O

X

-O

X радикал индивидуально представляет собой радикал, выбранный в группе, состоящей из водорода, алкила, содержащего 1-12 атомов углерода (например, метила, пропила, изопропила, бутила, изодецила, додецила и т.п.), фенила, толила и анизила, и n имеет величину 0-1; каждый у¹, у², z² и z³ индивидуально представляет собой радикал, выбранный в группе, состоящей из водорода, алкильного радикала, содержащего 1-18 атомов углерода, замещенного или незамещенного арила, алкарила, аралкила и алициклических радикалов, как определено и подтверждено примерами здесь выше (например, фенила, бензила, циклогексила, 1-метилциклогексила и т.п.), циано, галоида, нитро, трифторметила, гидроксила, а также карбонилокси, амино, ацила,фосфонила, оксикарбонила, амидо, сульфинила, сульфонила, силила, алкокси и тионила, как определено и подтверждено примерами здесь выше, а m имеет величину 2-6, более предпочтительно 2-4, а еще более предпочтительно 2. Предпочтительно как у¹, так и у² являются радикалами, имеющими стерическое затруднение изопропила, или более предпочтительно трет.-бутила, или более. Предпочтительно Q представляет собой метиленовую (СН₂) мостиковую группу, или алкилиденовую (-CH-R²-) мостиковую группу, где R² является алкилом, содержащим 1-12 атомов углерода, особенно метилом. Более предпочтительными лигандами являются лиганды формулы (А) выше, где оба у¹ и у² являются разветвленными алкилами, имеющими 3-5 атомов углерода, особенно трет.-бутилом, а z² и z³ являются водородом, алкилом, особенно трет.-бутилом, гидроксилом или алкоксильным радикалом, особенно метоксилом.In one embodiment, the phosphite ligands used in the present invention have the formula

PO

X

-O

X radical individually represents a radical selected in the group consisting of hydrogen, alkyl, containing 1-12 carbon atoms (e.g. methyl, propyl, isopropyl, butyl, isodecyl, dodecyl, etc.), phenyl, tolyl and anisyl, and n has a value of 0-1; each of y ¹ , y ² , z ² and z ³ individually represents a radical selected in the group consisting of hydrogen, an alkyl radical containing 1-18 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and alicyclic radicals, as defined and confirmed by the examples here above (e.g. phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl, etc.), cyano, halogen, nitro, trifluoromethyl, hydroxyl, as well as carbonyloxy, amino, acyl, phosphonyl, hydroxycarbonyl, amido, sulfinyl, sulfonyl , silyl, alkoxy and thionyl, as defined and confirmed by the examples here above, and m has a value of 2-6, more preferably 2-4, and even more preferably 2. Preferably both ¹ and ² are radicals having steric hindrance to isopropyl, or more preferably tert.-butyl , or more. Preferably, Q represents a methylene (CH ₂ ) bridging group, or an alkylidene (-CH-R ² -) bridging group, where R ² is an alkyl containing 1-12 carbon atoms, especially methyl. More preferred ligands are the ligands of formula (A) above, where both ¹ and ² are branched alkyls having 3-5 carbon atoms, especially tert.-butyl, and z ² and z ³ are hydrogen, alkyl, especially tert.- butyl, hydroxyl or alkoxyl radicals, especially methoxyl.

Other preferred phosphite ligands will include those in which X in the above formulas is a divalent radical selected in the group consisting of alkylene, especially ethylene, alkylene-hydroxyalkylene, especially —CH ₂ CH ₂ OCH ₂ CH ₂ -, and substituted or unsubstituted phenylene, naphthylene, naphthylene- (Q) n-naphthylene and phenylene- (Q) n-phenylene, where Q and n are the same as generally and preferably defined above. Among the more preferred bisphosphite type ligands when m is 2, there are those in which X is a divalent radical selected in the group consisting of 1,2-ethylene, naphthylene, substituted phenylene and substituted phenylene- (Q) n-phenylene, especially 1,4-naphthylene and 1,5-naphthylene. In addition, preferred substituents on such phenylene and / or phenylene- (Q) n-phenylene radicals are preferably radicals selected in the group consisting of alkyl and alkoxyl radicals, which most preferably correspond to substituent radicals at ¹ , ² , z ² and z3 defined here.

P-O-X-O-P

и

-O-X-O-P

где в указанных формулах (С) и (D) каждый из у¹, у², Q, X, z², z³ и n являются такими же, как в общем и предпочтительно определено в формулах (А) и (В) выше, а еще более предпочтительно n равно нулю. Разумеется, должно быть понятно, что каждый у¹, у², Q, z², z³ и n могут быть одинаковыми или различными в любом заданном фосфите. Более предпочтительно каждая у¹, у², z² и z³ группа индивидуально представляет радикал, содержащий 1-8 атомов углерода, замещенный или незамещенный арил, алкарил, аралкил и ациклические радикалы, как определено и подтверждено примерами здесь выше (например, фенил, бензил, циклогексил, 1-метилциклогексил и т.п.), циано, галоген, нитро, трифторметил, оксил, а также карбонилокси, амино, ацил, фосфонил, оксикарбонил, амидо, сульфинил, сульфонил, силил, алкокси и тионил, как определено и подтверждено примерами.Therefore, another preferred class of biophosphite ligands used herein are ligands of the formula:

POXOP

and

-OXOP

where in the indicated formulas (C) and (D) each of y ¹ , y ² , Q, X, z ² , z ³ and n are the same as generally and preferably defined in formulas (A) and (B) above , and even more preferably n is zero. Of course, it should be clear that each y ¹ , y ² , Q, z ² , z ³ and n can be the same or different in any given phosphite. More preferably, each of ¹ , ² , z ² and z ³ group individually represents a radical containing 1-8 carbon atoms, substituted or unsubstituted aryl, alkaryl, aralkyl and acyclic radicals, as defined and confirmed by the examples here above (for example, phenyl, benzyl, cyclohexyl, 1-methylcyclohexyl and the like), cyano, halogen, nitro, trifluoromethyl, oxyl, as well as carbonyloxy, amino, acyl, phosphonyl, hydroxycarbonyl, amido, sulfinyl, sulfonyl, silyl, alkoxy and thionyl, as defined and confirmed by examples.

Preferably, both ¹ and ² are radicals having steric hindrances to isopropyl or more preferably tert-butyl or more. More preferred ligands are those of the above, in which both ¹ and ² are branched chain alkyl radicals having 3-5 carbon atoms, especially tert-butyl, and z ² and z ³ are hydrogen, alkyl, especially tert. -butyl, hydroxyl or alkoxy, especially methoxy.

_X

P-O

X где Х является замещенным или незамещенным m-валентным углеводородным радикалом, R"' является таким же, как определено здесь в другом месте, каждый R^a независимо является замещенным или незамещенным одновалентным углеводородным радикалом, а и b каждый может иметь величину 0-6, при условии, что сумма a+b равна 2-6, а m равно a+b. Типичные третичные органополифосфиты могут включать бифосфиты, такие как имеющие формулу:

R

-O

X где R"' является двухвалентным органическим радикалом, как определено здесь в другом месте, а Х является замещенным или незамещенным двухвалентным углеводородным радикалом, а

P-O

X где каждый R^a независимо является замещенным или незамещенным одновалентным углеводородным радикалом, а Х является замещенным или незамещенным двухвалентным углеводородным радикалом; и
R

-O-X-O-P

где R"' является двухвалентным органическим радикалом, как определено здесь в другом месте, каждый R^a независимо является замещенным или незамещенным одновалентным углеводородным радикалом, а Х является замещенным или незамещенным двухвалентным углеводородным радикалом.Another group of phosphites that can be used in the present invention are tertiary organopolyphosphites. Such phosphites may contain two or more tertiary (trivalent) phosphorus atoms such as those that correspond to the formula

_X

PO

X where X is a substituted or unsubstituted m-valent hydrocarbon radical, R ″ is the same as defined here elsewhere, each R ^{a is} independently a substituted or unsubstituted monovalent hydrocarbon radical, and a and b may each have a value of 0-6, provided that the sum of a + b is 2-6 and m is a + b. Typical tertiary organopolyphosphites may include bisphosphites, such as those having the formula:

R

-O

X where R ″ is a divalent organic radical, as defined here elsewhere, and X is a substituted or unsubstituted divalent hydrocarbon radical, and

PO

X wherein each R ^{a is} independently a substituted or unsubstituted monovalent hydrocarbon radical, and X is a substituted or unsubstituted divalent hydrocarbon radical; and
R

-OXOP

where R ″ is a divalent organic radical, as defined here elsewhere, each R ^{a is} independently a substituted or unsubstituted monovalent hydrocarbon radical, and X is a substituted or unsubstituted divalent hydrocarbon radical.

R

-O

в приведенной выше формуле заменен

P O

где каждая Ar группа и Х и Q группы определены здесь в другом месте соответствующего контекста.Representatives of another class of biophosphites that can be used in the present invention are those in which

R

-O

in the above formula is replaced

PO

where each Ar group and X and Q groups are defined here elsewhere in the respective context.

где z⁵ является трехвалентным органическим радикалом, таким как описано более детально, например, в указанном ранее патенте США N 4567306.Another group of phosphites that can be used in the present invention are phosphites of the formula:
Z

where z ⁵ is a trivalent organic radical, such as described in more detail, for example, in the aforementioned US patent N 4567306.

 Finally, another group of phosphites that can be used in the present invention are triorganophosphites such as tris (ortho-phenyl) phenylphosphite, tris- (ortho-methyl) phenylphosphite, tris- (ortho-tert-butyl) phenylphosphite etc.

 Thus, the phosphite ligand used in the present invention may be a tertiary organophosphite ligand selected in the group consisting of mono-organophosphites, diorganophosphites, triorganophosphites and organopolyphosphites, such as described above.

 Additional typical examples of phosphite ligands useful in the present invention are shown in figures 1-4.

 Phosphite ligands of these types of general class applicable in the present invention, and / or methods for their preparation are known. For example, the phosphite ligands useful in the present invention can be easily and simply prepared using a series of conventional reactions of phosphorus halides with alcohols. Condensation reactions of this type and methods for their implementation are well known in the art. Some of these methods of preparation are given in US Pat. Billig et al. NN 4668651, 4717775, 4599207, 4769498 and in US patent 4774361 Mayer et al.

 The amount of ligand used is preferably sufficient to provide the desired anionic rhodium complex. Upon receipt or production of the target complex, an excess ligand source may be used, for example, to increase the rate of complex formation. Additionally, a free or uncomplexed ligand, for example, other than carbon monoxide, may be present during the hydroformylation step. The presence of such a free ligand can favorably affect the preservation of the active anionic rhodium-containing complex. The molar ratio of such a ligand (or source of ligand) to rhodium (or source of rhodium) is preferably in the range from about 0.1 to about 100, more preferably from about 0.5 to about 50, and even more preferably from about 0.5 to approximately 20. A very large excess of ligand source and free ligand should be avoided as harmful. Also, such a very large excess can have a destructive effect on the anionic rhodium-containing complex and / or on the hydroformylation stage.

The present anionic rhodium-containing complex is associated with a cation other than H ⁺ , and preferably with an alkali metal cation, more preferably with an organ-containing cation as described herein.

 In one embodiment, the rhodium-containing catalyst is derived from an anionic component that includes one or more such cations, preferably organo-containing cations. Such ionic components preferably have sufficient basicity, for example, include an anion having sufficient basicity to facilitate the formation of an anionic rhodium-containing complex. For example, such an anion may have sufficient basicity to completely deprotonate rhodium hydride, which can be provided or obtained, for example, as a precursor of the anionic rhodium-containing complex described herein. The particular anion is selected depending, for example, on the particular source of rhodium, the source of the ligand, the acid, if any, and the liquid medium used. Preferably, the ionic component is soluble in a liquid medium. Anions associated with medium and strong acid are one class of anions useful in true ionic components. Specific examples include halogens, sulfates, phosphates, carboxylates, in particular low molecular weight carboxylates such as formats, acetates, and the like.

Y

и

R

Y

где Y является поливалентным элементом группы Va периодической системы, в частности, выбран среди азота, фосфора и мышьяка, Y' является элементом VIa группы периодической системы, каждый из R⁷, R⁸, R⁹ и R¹⁰может быть одинаковым или различным и может быть объединен с образованием циклических структур. Например, каждый из R⁷, R⁸, R⁹ и R¹⁰может быть выбран среди водорода и углеводородных радикалов, которые могут быть замещенными или незамещенными и содержать по крайней мере один атом углерода, предпочтительно по крайней мере один, а более предпочтительно все углеводородные радикалы R⁷, R⁸, R⁹ и R¹⁰ содержат по крайней мере 4 атома углерода, например, от примерно 4 до 70 атомов углерода, а иногда примерно 4-20 атомов углерода. Однако по крайней мере один из R⁷, R⁸, R⁹ и R¹⁰ заместителей должен быть углеводородсодержащим.A preferred organo-cation may include an element from group Va or group VIa of the Periodic system. One specifically useful group of organo-containing cations are those that have a formula selected from

Y

and

R

Y

where Y is a polyvalent element of group Va of the periodic system, in particular selected from nitrogen, phosphorus and arsenic, Y 'is an element of group VIa of the periodic system, each of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and may be combined to form cyclic structures. For example, each of R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be selected from hydrogen and hydrocarbon radicals, which may be substituted or unsubstituted and contain at least one carbon atom, preferably at least one, and more preferably all hydrocarbon the radicals R ⁷ , R ⁸ , R ⁹ and R ¹⁰ contain at least 4 carbon atoms, for example, from about 4 to 70 carbon atoms, and sometimes about 4-20 carbon atoms. However, at least one of the R ⁷ , R ⁸ , R ⁹ and R ¹⁰ substituents must be hydrocarbon-containing.

 Hydrocarbon substituents may be aliphatic or aromatic and include, for example, n-hexyl, cyclohexyl, phenyl, benzyl, naphthyl, and the like. Examples of quaternary ammonium or quaternary phosphonium tetrauglevodorodammoniynye fragments are fragments, e.g., tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, tetra-izobutilammony, trimethylbutylammonium, tetrageptilammony, atsetiltimetilammony, tetrafenilammony, trimethylbenzylammonium, tetrabenzilammony, tetradodetsilam- mony, tetraoktadetsilammony etc. trihydrocarbon ammonium fragments, for example, trimethylammonium, triethylammonium, triphenylammonium, tridecylammonium, trioctadecylammonium, and the like. dihydrocarbon hydrocarbon ammonium fragments, for example, dimethyl ammonium, diethylammonium, di-n-butylammonium, di-n-heptylammonium, diphenylammonium, dibenzylammonium, didodecylammonium, dioctadecylammonium, etc. hydrocarbon ammonium moieties, for example methyl ammonium, n-butyl ammonium, dodecylammonium, octadecylammonium, phenylammonium, benzylammonium, and the like. tetrahydrocarbonphosphonium moieties, e.g. tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetra-n-butylphosphonium, tetraisobutylphosphonium, trimethylbutylphosphonium, tetraphenylphosphonophosphonium, tetraphenylphosphonophosphonium, tetraphenylphosphonophonethe trihydrogenphosphonium moieties, for example, trimethylphosphonium, triethylphosphonium, triphenylphosphonium, tridedecylphosphonium, trioctadecylphosphonium and the like. dihydrocarbon phosphonium moieties, for example, dimethylphosphonium, diethylphosphonium, di-n-butylphosphonium, di-n-heptylphosphonium, diphenylphosphonium, dibenzylphosphonium, didodecylphosphonium, dioctadecylphosphonium and the like. hydrocarbonphosphonium moieties, e.g. methylphosphonium, n-butylphosphonium, dodecylphosphonium, octadecylphosphonium, phenylphosphonium, benzylphosphonium and the like.

Another group of organo-containing cations includes bis- (hydrocarbon-phosphine) iminium of the general formula:
[(R ₃ ¹¹ P) ₂ N] ⁺ where each R ¹¹ may be the same or different and may be the same as indicated for R ⁷ -R ¹⁰ . Examples of bis- (hydrocarbonphosphine) iminiums are bis- (triphenylphosphine) iminium, bis- (tribenzylphosphine) iminium, bis- (trimethylphosphine) iminium, bis- (tridecylphosphine) iminium, and the like. and mixtures thereof.

Another group of organo-containing cations has the formula:
[(R ¹³ ) ryR ¹² -y- (R ¹³ ) r) ²⁺ where R ¹² is alkylene with 1-6 carbon atoms, each R ^{13 is} independently selected from hydrogen and hydrocarbon radicals, which may be substituted or unsubstituted, and r is 3. Typical examples of this group include quaternized diamines, quaternized diphosphines, and the like. Specific members of this group include
N, N'-bis (trimethyl) propylene diammonium,
N, N'-bis (triphenyl) propylene diammonium,
N, N'-bis (trioctadecyl) propylene diammonium,
P, P'-bis (trimethyl) propylene diphosphonium and the like. and mixtures thereof.

 The amount of the ionic component, for example, organo-containing cations, used in the preparation of the present catalytic compositions, can be very dependent on, for example, the specific ionic component used and on the target rhodium-containing catalyst. The molar ratio of the ionic component to rhodium used in the preparation of the present catalyst compositions can vary within wide limits, for example, in the range of from about 0.1 to about 100. The amount of cations present should preferably be at least sufficient to combine or combine with the rhodium-containing compound for example, a rhodium-containing anion to produce the desired catalyst. An excess of cation may be used, for example of the order of at least about 50-100% or more.

In one embodiment, the present epoxide hydroformylation reaction occurs in the presence of an electrophile, for example, H ⁺ ions, protic acids, Lewis acids, and the like. and mixtures thereof, in particular H ⁺ ions, in an amount effective to further promote hydroformylation of the epoxide. A certain amount of H ⁺ ions may be present as a result of the deprotonization of the rhodium hydride compound described herein. In some cases, this amount of H ⁺ ions may be sufficient to provide further promotion of hydroformylation of epoxides. In a particularly useful embodiment, the hydroformylation of the epoxide occurs in the presence of an acid, preferably a protic acid, which may be included in the catalyst composition or the catalyst precursor composition.

 Medium or strong acids are preferred for use in the present invention. Suitable acids for the process of the present invention are strong acids such as sulfuric acid, phosphoric acid, hydroiodic acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, p-toluenesulfonic acid, and the like. and mixtures thereof. Medium acids suitable for the process include carboxylic acids such as benzoic acid, acetic acid, propionic acid, acid salts such as sodium hydrogen phosphate and the like. and mixtures thereof. Phosphoric acid is a specific example of a beneficial acid. The amount of acid used is sufficient to further promote or facilitate hydroformylation of the epoxide. This amount may vary, for example, depending on the particular acid and the anionic rhodium complex used. The molar ratio of acid to rhodium may be in the range of from about 0.1 to about 10, preferably about 0.2-3.

 The present rhodium-containing catalysts are preferably substantially free of alkali metal ions. Indeed, the present process for producing 1,3-diol / aldehyde, in particular the hydroformylation step itself, is preferably carried out practically in the absence of alkali metal ions.

 The conditions under which the catalyst composition is prepared are such that a desired rhodium-containing catalyst is formed. This preferably takes place in a liquid medium, which preferably acts as a solvent for the rhodium-containing catalyst and which more preferably acts as a solvent for the rhodium source, ligand source, ionic component and acid, if any, and for other components, if any, in the precursor used to obtain a rhodium-containing catalyst. In one particular useful embodiment, the liquid medium used in the catalyst precursor composition has substantially the same chemical composition as the liquid medium used in the epoxide hydroformylation reaction step.

 The conditions under which the catalyst composition is prepared may be similar to those used in the hydroformylation step. The catalyst composition can be prepared separately and outside the epoxide hydroformylation step, and then introduced to this step to provide the desired promotion of the catalytic hydroformylation. In one embodiment, a catalyst precursor composition is formed and this catalyst precursor composition is introduced into the epoxide hydroformylation step. Hydroformylation conditions are effective for forming a catalyst composition from this precursor.

 The molar ratio of carbon monoxide to hydrogen used in the epoxide hydroformylation step can vary significantly and can range from about 0.1 to about 10.

 In one embodiment, the present process for producing 1,3-diol and / or 3-hydroxyaldehyde is to contact a combination of epoxide, carbon monoxide and hydrogen in the presence of a catalyst composition effective to promote hydroformylation of the epoxide and a promoter component under conditions effective to form at least one of 1,3-diol and 3-hydroxyaldehyde. The catalyst composition consists of a ligand-containing anionic rhodium-containing complex and an electrophile. The promoting component may be selected among compounds, complexes, polymeric materials, mixtures thereof, and the like. Such a promoter component is present in an amount effective to increase the hydroformylation rate of the epoxide and / or to increase the selectivity of the formation of 1,3-diol and / or 3-hydroxyaldehyde. Such an increase or increase is relative to a substantially identical process of hydroformylation of the epoxide, carried out without or with the practical absence of a promoter component or components useful in the present case.

Any promoter component or components can be used in the present invention, provided that such component or components are used in concentrations that provide one or more of the increases noted here, their concentration preferably meets the criteria for equivalent pH given here. The promoter component is preferably in the material used in the present contacting step, for example, in the reaction mixture in a molar concentration e.g., as much moles per liter of liquid is theoretically or equivalent pH of an aqueous liquid at ²² ° C containing only such molar concentration of such promoter component is in the range from about 1 to about 12, more preferably about 1.6-10.7. The promoter component is in a concentration that provides the above theoretical or equivalent pH values, as was found to increase at least the epoxide hydroformylation rate and selectivity in 1,3-diol and 3-hydroxyaldehyde. Without wishing to limit the invention to any particular theory of work, it is believed that such promoter components can act to facilitate the formation and / or maintain an effective concentration of the ligand-containing anionic rhodium-containing complex of the catalyst composition under contact conditions. In contrast, components or concentrations of components that result in either a too high or too low a theoretical or equivalent pH, as defined herein, cannot effectively alleviate, but in fact can inhibit, the formation and / or maintenance of an effective concentration of anionic rhodium-containing complexes. In any case, the promoter component is present in an amount to provide the aforementioned theoretical or equivalent pH values, which, as has been found, should favor the present contacting step of the hydroformylation reaction.

 Although water meets the equivalent pH criterion and can be used as a promoting component, the presence and water can irreversibly decompose or degrade one or more components of the present catalyst composition under conditions of hydroformylation of epoxides and / or otherwise worsen the effect of the present process and composition, for example, destructively affect the activity and / or stability of the catalyst composition. The present promoter components are preferably selected so that there is no doubt that there is no deteriorating effect on the present process and composition, in particular that there is no irreversible decomposition or degradation of one or more components of the present catalyst composition under conditions of hydroformylation of epoxides. So, the promoter component should preferably be other than water.

In one embodiment, the promoter component is selected among those components that alone or in combination with H ⁺ form a hydrogen bond with one or more ligands present during the epoxide hydroformylation reaction.

 As used here, the term "promoting component" refers not only to components that are effective for increasing the hydroformylation rate of epoxides and / or selectivity of hydroformylation of epoxides to 1,3-diol and / or 3-hydroxyaldehyde, but also to one or more materials, capable of forming one or more of these compounds under conditions of hydroformylation of epoxides.

 Particularly useful promoter components are those selected from (a) nitrogen-containing compounds, (b) compounds containing hydroxyl groups, (c) compounds containing carboxyl groups, (d) protic acids and mixtures thereof. A promoter component or components may include at least one component that is at least two of (a), (b), (c) and (d). Especially useful results are obtained when the promoting component comprises one hydroxyl group and / or at least one carboxyl group.

 Among the useful nitrogen-containing components are amines, amides, imines, imidazoles, etc., and mixtures thereof. Polymer nitrogen-containing compounds and mixtures thereof, in particular those polymeric nitrogen-containing compounds that are substantially soluble in the liquid medium present during the hydroformylation reaction, can also be used as promoter components. The nitrogen atom or atoms of nitrogen-containing compounds may be part of a heterocycle or substituted heterocycle, for example, containing 4.5 or 6 or more carbon atoms, and / or may have one or more such cycles and / or one or more saturated, unsaturated or aromatic hydrocarbon groups or substituted hydrocarbon groups linked, for example, by covalent bonds to each other. The nitrogen-containing compound may contain one or more than one nitrogen atom. In useful monomeric nitrogen-containing compounds, the number of nitrogen atoms is preferably in the range of 1-5, more preferably 1-3. Compounds with one nitrogen atom provide useful results. Preferably, at least two, and more preferably all three bonds of at least one of the nitrogen atoms are bonded to hydrocarbon or substituted hydrocarbon groups.

 Such hydrocarbon groups and substituted hydrocarbon groups may contain any number of carbon atoms, provided that the promoter component acts as described in the present invention. In one embodiment, such hydrocarbon and substituted hydrocarbon groups contain 1-20, preferably 1-12 carbon atoms. Examples of useful hydrocarbon groups include alkyl, such as methyl, ethyl, propyl, butyl, octyl, decyl and the like. aralkyl such as phenylmethyl, phenylethyl, phenylbutyl, phenylloctyl and the like. aralkenyl such as phenylethenyl, phenylbutenyl, phenylloctenyl and the like. alkenyl such as ethenyl, propenyl, butenyl, octenyl, decenyl and the like. alkylene, such as methylene, ethylene, butylene, pentylene, hexylene and the like. other divalent hydrocarbon groups, aryl such as phenyl, naphthyl and the like. alkaryl such as methyl phenyl, ethyl phenyl, butyl phenyl, octyl phenyl and the like. alkenaryl such as ethenyl phenyl, butenyl phenyl, octenyl phenyl and the like. and similar groups. Substituted counterparts of such hydrocarbon groups may be used. Such substituents may include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, and the like. and mixtures thereof.

 Specific useful examples of nitrogen-containing promoters, especially for increasing the hydroformylation rate of ethylene oxide, include tris (4-bromophenyl) amine, triphenylamine, benzimidazole, 2,6-lutidine, 2-methylimidazole, 1-methylimidazole, 1,8-bis- (dimethyl- amino) naphthalene, triethanolamine, N-methyl-pyrrolidone, dimethylformamide and the like. and mixtures thereof.

 Among the useful promoting components that contain hydroxyl groups, there are compounds in which the hydroxyl group or groups are combined with a saturated, unsaturated or aromatic hydrocarbon or substituted hydrocarbon group. Such hydrocarbon groups and substituted hydrocarbon groups may contain any number of carbon atoms, provided that the promoter component acts as described in the present invention. In one embodiment, such hydrocarbon or substituted hydrocarbon groups contain 1-20, preferably 1-12 carbon atoms. Examples of useful hydrocarbon groups include those groups as described herein for nitrogen containing compounds useful as promoter components. Substituted duplicates of such hydrocarbon groups may be used. Such substituents may include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, and the like. and mixtures thereof.

 Enolysable dicarbonyl compounds, such as 1,4-pentanedione and ethyl acetoacetate, which exist as two equilibrium tautomers (one of which includes a hydroxyl group), may also be useful as promoters.

 Particularly useful compounds containing a hydroxyl group are selected among such compounds having at least one aromatic hydrocarbon group. Polymer compounds and mixtures thereof, which include one or more hydroxyl groups, especially those polymers which are practically soluble in the liquid medium present during the epoxide hydroformylation reaction, can also be used as promoter compounds. Compounds containing hydroxyl groups may include one or more than one hydroxyl group. In monomeric compounds containing a hydroxyl group, the number of hydroxyl groups is preferably in the range from 1 to about 6; more preferably 1-4.

 Special examples of compounds containing hydroxyl groups useful as promoter components include phenol and phenol derivatives such as alkyl, aryl and aralkyl substituted derivatives, for example, o-, m- and p-cresols, dimethylphenols, ethyl phenols, butylated oxytoluene and etc. diphenol and diphenol derivatives such as alkyl and aryl substituted; substituted diphenols, catechol and catechol derivatives; resorcinol and resorcinol derivatives, benzene triol and benzene triol derivatives such as 1,2,4-benzene triol; oxynaphthalenes such as 2-naphthol; dioxinaphthalenes such as 1,3-dioxinaphthalene; etc. and mixtures thereof.

 Among the useful promoting compounds that contain a carboxyl group or groups, there are those in which the carboxyl group or groups are attached to a saturated or unsaturated or aromatic hydrocarbon or substituted hydrocarbon group. Such hydrocarbon groups and substituted hydrocarbon groups may contain any number of carbon atoms, provided that the promoter component functions as described in the present invention. In one embodiment, such hydrocarbon or substituted hydrocarbon groups contain 1-20, preferably 1-12 carbon atoms. Examples of useful hydrocarbon groups include groups as exemplified herein with respect to nitrogen containing compounds useful as promoter compounds. Substituted duplicates of such hydrocarbon groups may be used. Such substituents may include, for example, carbon, hydrogen, oxygen, nitrogen, sulfur, halogen, phosphorus, and the like. and mixtures thereof.

 Particularly useful compounds containing carboxyl groups are selected among those compounds having at least one aromatic hydrocarbon group, for example, as described. Polymer compounds and mixtures thereof, which include one or more carboxyl groups, especially those polymers which are substantially soluble in the liquid medium present during the epoxide hydroformylation reaction, can also be used as promoter compounds. Compounds containing carboxyl groups may contain one or more carboxyl groups. In monomer compounds containing carboxyl groups, the amount of carboxyl groups is preferably in the range from 1 to about 6, more preferably 1-4.

 Specific examples of compounds containing carboxyl groups useful as promoter components include polycarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valerianic acid, isovaleric acid, hexanoic acid, decanoic acid, lauryl acid, stearic acid, acrylic acid, lactic acid, benzoic acid, p-ethoxybenzoic acid, 3,5-dimethoxybenzoic acid, picolinic acid, pipercolic acid, cinnamic acid; dicarboxylic acids such as adipic acid, 1,2-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, tartaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid and 1,8-naphthalenedicarboxylic acid; polycarboxylic acids such as polyacrylic acid and 1,3,5-benzenetricarboxylic acid and the like. and mixtures thereof.

 Protonic acids, preferably used in concentrations sufficient to satisfy the equivalent pH criterion given above, are effective as promoter components. Strong acids, medium acids and weak acids can all be used. Acid salts and other compounds that form protonic acids can also be used, for example, under contacting conditions. Strong protonic acids, in particular acids that are as strong as or stronger than phosphoric acid, can be used in the present invention. Suitable strong acids include sulfuric acid, phosphoric acid, hydroiodic acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, p. Toluenesulfonic acid, and the like. and mixtures thereof. Phosphoric acid is a specific example of a beneficial acid.

 Useful protonic acids of medium strength include the previously mentioned carboxylic acids, as well as phosphorous acid, sulfuric acid, phosphinic acid, phosphonic acid, nitrous acid, and the like. Relatively high concentrations of proton acids of medium and weak strength are advantageous in comparison with the concentrations of the strong acids used. Examples of weak proton acids that can be used include diphenol, phenol, butylated oxytoluene, succinimide, carbonic acid, ammonium salts, and the like.

 The promotion component may include one or more than one of the other electronically repulsive groups. Examples of electron repellent groups useful in the present invention include aromatic hydrocarbon groups, which include both substituted and unsubstituted aromatic groups; fluoroalkyl such as trifluoromethyl and difluoroethyl; fluoroaryl such as fluorophenyl; nitro; chlorine; bromine; iodine; carbonyl groups; ester groups; amide groups; carboxyl groups; cyano; ammonium (including hydrocarbon and substituted hydrocarbon ammonium) groups; phosphonium (including hydrocarbon and substituted hydrocarbon phosphonium) groups; sulfonium (including hydrocarbon and substituted hydrocarbon) groups and the like. and mixtures thereof.

 A useful aromatic hydrocarbon group or groups include at least one aromatic hydrocarbon ring, for example, groups such as aryl, alkaryl, alkenylaryl, aralkyl, aralkenyl, substituted duplicates thereof, mixtures thereof and the like, mentioned elsewhere herein. Groups that include one or more fused aromatic ring structures are also within the scope of the present invention.

 The promoter component may include one or more electron-donating groups. Examples of electron donor groups useful in the present invention are alkyl groups such as methyl ethyl, propyl and butyl; phenyl groups, alkyl phenyl groups such as methyl phenyl, ethyl phenyl, propyl phenyl and butyl phenyl; alkoxyphenyl groups such as methoxyphenyl, ethoxyphenyl and propoxyphenyl; aminophenyl groups such as aminophenyl, methylaminophenyl, dimethylaminophenyl and methyl, ethylaminophenyl; oxyphenyl groups such as oxyphenyl and dioxiphenyl; amidophenyl and the like. and mixtures thereof.

 As used here, the electron repellent ability and electron donor ability of any given group or substituent is compared to a substituent of a hydrogen atom in the process of hydroformylation of epoxides. Those. an electron repulsive group is defined as capable of more strongly repelling electrons relative to a substituent of a hydrogen atom. Similarly, an electron-donating group is defined as being capable of more easily donating one or more electrons to a substituent of a hydrogen atom, and the like.

 The inclusion of one or more electron repellent groups and / or electron donor groups may act to control the acidity (basicity of a particular component, so that it is possible to match the acidity) with the basicity of the present promoting components.

 Particularly useful promoter components are selected from triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, diphenol, catechol, isophthalic acid, picolinic acid, acetic acid, p-ethoxybenzoic acid, dimethylformamide, N-methylpyrrolidone and theirs.

The amount of promoter component used should be sufficient to provide the desired results and preferably to satisfy the equivalent pH criterion given here. Care should be taken to avoid excessive amounts of the promoting component. Such excess amounts of the promoter component may provide little or no additional benefits and / or may have a generally degrading effect on the present system. Also, the cost of the promoting component can facilitate its use in large quantities. In one useful embodiment, the promoter component is in such an amount that the molar ratio of the promoter component to rhodium is in the range from about 0.1 to about 10. In particular, the molar ratio of nitrogen atoms, hydroxyl groups, carboxyl groups and / or H ⁺ found in the promoter component, rhodium is in the range from about 0.1 to about 10.

 The 3-hydroxyaldehyde obtained by hydroformylating an epoxide can be extracted, for example, using one or more conventional techniques, from a liquid medium and other components that are present during or after the hydroformylation reaction. Then 3-hydroxyaldehyde can be hydrogenated, for example, using a conventional hydrogenation process to obtain the desired 1,3-diol.

The hydrogenation step is usually carried out under certain conditions of time and temperature. Preferably, hydrogenation temperature is in the range of from about 90 to about 170 ^C, preferably for from about 0.5 to about 4 hours. The hydrogenation reaction can be carried out both in the presence and absence of a hydrogenation liquid medium. The liquid hydrogenation medium is preferably water, although non-reactive polar organic solvents such as dimethoxyethane and the like can be used. The pressure applied during hydrogenation is preferably in the range of from about 500 lb / ⁱⁿ² (35.15 kg / cm ²⁾ to about 2000 lbs / ⁱⁿ² (140.6 kg / cm ^2). The catalyst used in the hydrogenation step may be any well-known hydrogenation catalyst used in the art, such as Raney nickel, palladium, platinum, ruthenium, rhodium, cobalt and the like. It is desirable to use metal or a metal compound as a hydrogenation catalyst, which can be easily and economically prepared, which have a high degree of activity and which retain this activity for a long period of time. The hydrogenation catalyst may be used in finely divided form and dispersed in the reaction mixture, or it may be used on a carrier such as diatomaceous earth, clay, alumina, coal, and the like. The amount of hydrogenation catalyst used is preferably in the range of from about 0.1 to about 10%, more preferably about 1-8 wt. from hydrogenated 3-hydroxyaldehyde.

Лиганд II

Лиганд III

Лиганд IV

П р и м е р 1. Синтезируют предшественник катализатора гидроформилирования при объединении 0,52 г родийдикарбонилацетилацетоната (Rh(CO)₂ (ацац)), 0,643 г тетрабутилфосфонийацетата (Bu₄P)(OAc), 1,693 г Лиганда IV и 5 см³ воды в 80 см³ диметоксиэтана. Этот предшественник катализатора испытывают следующим образом.In the examples, these names are used to denote the following ligands:
Ligand I

Ligand II

Ligand III

Ligand IV

Example 1. A hydroformylation catalyst precursor is synthesized by combining 0.52 g of rhodium dicarbonyl acetylacetonate (Rh (CO) ₂ (acac)), 0.643 g of tetrabutylphosphonium acetate (Bu ₄ P) (OAc), 1.693 g of Ligand IV and 5 cm ³ water in 80 cm ^{3 of} dimethoxyethane. This catalyst precursor is tested as follows.

Autoclave of 300 cm ^3, equipped with stirring, made from a suitable stable metallic alloy such as stainless steel or Hastelloy C ^R, provided with an internal cooling coil, thermocouple and a pressure measuring device is used for testing. The catalyst precursor and ethylene oxide are mixed in a Schlenk vessel, and then pressed into the autoclave through a valve at the top of the autoclave. Then the autoclave is set to its working position and the appropriate amounts of carbon monoxide and hydrogen are introduced. Then the autoclave is heated to the desired temperature and the pressure is set as necessary to maintain the desired pressure with an additional supply of a mixture of CO / H ₂ or by blowing. As the hydroformylation reaction proceeds, additional amounts of CO / H ₂ mixture are introduced until the desired gas consumption or reaction time is reached. After completion of the reaction, the autoclave ohlazhlayut, e.g., to -40 ^{° C,} and the excess gas vented. After warming ^to 0 ° C the autoclave was opened and its contents analyzed by conventional methods.

When using the above catalyst precursor contacted 10 g of ethylene oxide in an autoclave at ¹¹⁰ ° C and a pressure of 1100 lbs / inch (77.3 kg / cm ²⁾ synthesis gas, CO / H ₂ mixture having a molar ratio of 1 CO to 2 H ₂ . The feed gas begins to be consumed almost immediately and there is no induction period.

 This reaction results in the selectivity of ethylene oxide to 3-hydroxypropionaldehyde and 1,3-propanodiol 44% mol. The rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol is 0.33 moles / l / h.

 PRI me R 2. Repeat example 1 with the exception that the catalyst precursor is synthesized without water and dimethoxyethane is replaced by tetraglim. This reaction results in the selectivity of ethylene oxide to 3-hydroxypropionaldehyde and 1,3-propanediol 38 mol. and a formation rate of 3-hydroxypropionaldehyde and 1,3-propanediol of 0.19 mol / l / h. These results indicate that water can have an enhancing effect on the activity and selectivity of the catalyst composition or system.

Example 3 Example 1 is repeated with the exception that tetrabutylphosphonium acetate, (Bu ₄ P) (OAc)) is not used. Virtually no hydroformylation of ethylene oxide is observed. These results show that the ionic component is essential for an effective catalytic system for hydroformylation of epoxides.

 EXAMPLES 4 and 5. Repeat example 2 with the exception that use Ligand III (example 4) and Ligand 1 (example 5) instead of Ligand IV, and the hydroformylation reaction is carried out with a half concentration of the catalyst precursor with respect to concentration in example 2.

 The results of these tests are given in table 1.

 These results show that various bis-phosphite ligands are useful for preparing a catalyst system for hydroformylating epoxides.

 Example 6 Example 2 is repeated with the exception that the hydroformylation reaction is terminated when only 25% of ethylene oxide enters the reaction. As a result, in Example 6, ethylene oxide selectivity to 3-hydroxypropionaldehyde and 1,3-propanediol of 75% mole was obtained. and the rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol 0.8 mol / l / h. These results show that a reduced conversion of the epoxide provides an increase in the rate of formation of the product and an increase in selectivity in the target product or products.

Example Example 7 Example 2 was repeated with the exception that toluene is used instead of tetraglyme, the reaction temperature is 115 ^C and the reaction mixture was introduced 2 mmol of 2,6-lutidine. The molar concentration of 2,6-lutidine is such that the equivalent pH of the 2,6-lutidine / water solution is about 9.5. Significant hydroformylation of ethylene oxide occurs, a significant amount of 3-hydroxyaropionaldehyde is formed. When opening the autoclave, it is determined that the obtained 3-hydroxypropionaldehyde forms a separate phase from the toluene solution.

19.5 moles of the obtained 3-hydroxypropionalaldehyde are separated from the toluene solution. This separated 3-hydroxypropionaldehyde is added to 10 ml of water and transferred via a glass line to a 300 ml autoclave. 0.27 g of Raney 3100 molybdenum promoted nickel catalyst in 30 ml of water are added to this autoclave. Set the pH to 7 by adding 3 N. sulfuric acid. The autoclave was sealed and pressurized to 1000 lbs / ⁱⁿ² (70.3 kg / cm ²⁾ of hydrogen at 20 ^C. The contents were heated to 105 ^{° C} and kept at this temperature for 3 hours. The reaction mixture was cooled ^to 20 ° C and analyzed content. Found that 1,3-propanediol is formed with a yield of 96%
Significant activity of the present catalyst composition for promoting the hydroformylation of ethylene oxide in toluene was unexpected, since in another work, namely, Marty et al. US patent N 4873378 and 4873379, it is indicated that solvents such as toluene are unsuitable for hydroformylation of low molecular weight epoxides. The present system, in particular the real catalytic system, differs significantly from this other work and provides unexpected advantages over it.

PRI me R 8. Download 1.0 g of Rh ₄ (CO) ₁₂ and 4.44 g of Ligand IV in a Parra autoclave with a capacity of 300 cm ³ . The autoclave is sealed and then purged with nitrogen. The autoclave pressure is applied of 40 cm ³ of heptane through the corresponding valve and washed with a strong flow of the gas mixture of 1: 1 CO / H ₂ before by pressure of this gas mixture to a pressure of 60 lbs / ^in2. The autoclave is stirred overnight at room temperature. Then the autoclave is opened and a whitish precipitate is collected and washed with hexane and dried in vacuum. The product is defined as HRh (CO) ₂ (Ligand IV).

To a stirred mixture of 0.3 g of potassium hydroxide in 30 cm ^{3 of} methanol in nitrogen was added 1.0 g of HRh (CO) ₂ (Ligand IV), then 23 g of bis (triphenylphosphine) iminium chloride, (PPN) (Cl). The mixture was stirred at room temperature for 5 hours, after which the insoluble product was filtered off. It is washed with methanol, diethyl ether and then dried in vacuo. This product is defined as (PPN) (Rh (CO) ₂ (Ligand IV)).

Example 2 is repeated with the exception that 1 mmol (PPN) (Rh (CO) ₂ (Ligand IV)) is used as a catalyst precursor. There is practically no gas consumption after 50 minutes. Virtually no H + ions are present during the hydroformylation reaction.

 PRI me R 9. Repeat example 8 with the exception that 0.06 g of acetic acid is introduced into the autoclave. The molar concentration of acetic acid is such that the equivalent pH of the acetic acid / water solution is about 3.4. As a result of these tests, the selectivity of ethylene oxide to 3-hydroxypropionaldehyde and 1,3-propanediol 26 mol. and the rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol is 0.05 mol / l / h. These results indicate that the presence of acetic acid at the above concentration may promote hydroformylation of epoxides.

Example 10 Example 8 is repeated with the exception that the equivalent amounts of (PPN) (Rh (CO) ₂ (Ligand IV)) and (HRh (CO) ₂ (Ligand IV)) are used instead of only (PPN) (Rh (CO) ₂ (Ligand IV)) and a molar ratio of CO to H ₂ of 0.25. The results of this experiment give an ethylene oxide selectivity of 3-hydroxypropionaldehyde and 1,3-propanediol of 37 mol. and the rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol of 0.055 mol / l / h.

PRI me R 11 (comparative). A hydroformylation catalyst precursor is synthesized by combining 0.51 g of rhodium dicarbonyl acetate, Rh (CO) ₂ (acac), 0.53 g of tricyclohexylphosphine, (Cy) ₃ P, 0.13 g of phosphoric acid, H ₃ PO ₄ , 5 cm ^{3 of} water and 0.1 g of hydroquinone in 80 g of tetraglyme solvent. This formulation is essentially the same as described in Example 6 of US Pat. No. 4,873,378 to Marfy et al.

 Example 1 is repeated using the catalyst precursor prepared above instead of the catalyst precursor prepared in Example 1. An induction period of about 30 minutes is observed before gas consumption begins. During this induction period, it is believed that the catalyst precursor reacts with ethylene oxide to form an active ethylene oxide hydroformylation catalyst, which itself includes ethylene oxide molecules and / or one or more parts of it. As a result of this experiment, a selectivity of 3-hydroxypropionaldehyde and 1,3-propanediol of 59% and a rate (not including the induction period) of the formation of 3-hydroxypropionaldehyde and 1,3-propanediol of 0.08 mol / l / h are obtained. In Example 11, 1,3-propanediol is obtained in a greater amount than 3-hydroxypropionaldehyde, while the converse is true for Example 1.

PRI me R s 12-15. A series of rhodium-containing catalyst precursors is prepared. Each of these catalyst precursors is prepared by combining the following components in 80 cm ^{3 of} dimethoxyethane. Each of these catalyst precursors is prepared using 2 mmol of rhodium dicarbonyl acetylacetonate, Rh (CO) ₂ (acac), 2 mmol of tetrabutylphosphonium acetate, (Bu ₄ P) / (OAc), 2 mmol of phosphoric acid, H ₃ PO ₄ and 5 cm ^{3 of} water. These catalyst precursors include the following ligands:
Example Ligand Amount of Ligand
12 Ligand II 2 mmol
13 P / Me ₃ ⁽¹⁾ 2 mmol
14 P (OMe) ₃ ⁽²⁾ 2 mmol
15 Bu ^t NC ⁽³⁾ 2 mmol
(1) Trimethylphosphine
(2) Trimethylphosphite
(3) Tert-butylisonitrile.

Each of these catalyst precursors is tested in the ethylene oxide hydroformylation reaction using the procedure described generally in Example 1. The molar concentration of phosphoric acid is such that the equivalent pH of the phosphoric acid / water solution is about 1.8. Contacting is performed under the following conditions: Pressure 1000 psi ²
(70.3 kg / cm ² ) Temperature 110 ^о С СО / Н ₂ (molar) 1: 2 Concentration of rhodium 2000 ppm million.

 The results of these tests are presented in table.2.

 These results show that phosphite ligands (examples 12 and 14) provide increased selectivity to the product compared to non-phosphite ligands (examples 13 and 15). Referring to example 1, bis-phosphite ligands provide highly effective rates of product formation and selectivity compared to other phosphite ligands and non-phosphite ligands.

PRI me R s 16-31. Prepare another series of rhodium-containing compositions. Each of these catalyst precursors is prepared by combining the following components in 80 cm ^{3 of} tetraglim. Each of the catalyst precursors was prepared using 2 mmol of rhodium dicarbonyl acetylacetonate, Rh (CO) ₂ (acac), 2 mmol of tetrabutylphosphonium acetate, (Bu ₄ P) (OAc), and 2 mmol of the ligand indicated below.

 Each of the catalyst precursors was tested in the ethylene oxide hydroformylation reaction according to the procedure of Example 1.

For these exceptions specifically contacting is carried out under the following conditions: pressure of 1000 lbs / ⁱⁿ²
(70.3 kg / cm ² ) Temperature 110 ^о С Со / Н ₂ (molar) 1: 2
The concentration of rhodium is 2000 ppm. Water 5 cm ³
The test results are shown in table.3.

 These results show that the choice of ligand is essential in obtaining an effective epoxide hydroformylation catalyst.

PRI me R s 32-43. Example 2 is repeated twelve times with the exception that 2 mmoles of various nitrogen-containing compounds, as described below, are included in the catalyst. These catalyst precursors are also tested in the hydroformylation of ethylene oxide at 115 ^{° C} and a pressure of 900-1000 lb / ⁱⁿ² (63,3-70,3 kg / cm ²⁾ of a mixture of synthesis gas having a molar ratio of 1 CO to 4.3 H ₂ .

 The following results are obtained in these tests (table. 4).

 The results show that certain amounts of certain nitrogen-containing compounds affect the selectivity and / or rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol during hydroformylation of ethylene oxide. In particular, the presence of such compounds in amounts such that the equivalent pH is about 12 or lower, preferably about 10.7 or lower, provides an increased rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol. The presence of such amounts of certain nitrogen-containing compounds also provides increased selectivity of ethylene oxide to 3-hydroxypropionaldehyde and 1,3-propanediol. As for example 43, it is believed (without wanting to limit the invention to any particular theory of operation) that 1,3-bis-dimethylamino / naphthalene, for example, due to the steric hindrance inherent in this compound, acts as a less basic component than it was predicted using equivalent pH. Therefore, although the equivalent pH is slightly higher than 12, 1,8-bis (dimethylamino) naphthalene should provide some degree of increase in the rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol.

 PRI me R s 44-49. A series of experiments was carried out to hydroformylate ethylene oxide in accordance with the general procedure of Example 1 in the absence of water.

The catalyst precursor used is:
2 mmol of rhodium dicarbonyl acetylacetonate
5 mmol Ligand IV
3 mmol tetrabutylphosphonium acetate
3 mmol of 2,6-lutidine
Use 100 cm ^{3 of} tetraglim as a solvent.

The molar concentration of 2,6-lutidine is such that the equivalent pH of the solution of 2,6-lutidine in water should be about 9.6. The reaction conditions are: pressure of 1000 lbs / ⁱⁿ²
(70.3 kg / cm ² ) Temperature 115 ^о С
The molar ratio of CO / H ₂ 1: 2
Ethylene oxide: varies as follows.

 The following experimental results were obtained (Table 5).

 These results indicate that ethylene oxide concentration affects the activity and selectivity of the catalyst system.

 EXAMPLES 50 and 51. Two experiments were carried out to hydroformylate ethylene oxide in accordance with the general procedure of Example 1 in the absence of water.

As a catalyst precursor, use:
2 mmol of rhodium dicarbonyl acetylacetonate
2 mmol Ligand IV
2 mmol tetrabutylphosphonium acetate
Phosphoric acid changes as follows.

Use 100 cm ^{3 of} tetraglim as a solvent. The reaction conditions are as follows: Pressure: 1000 lbs / ⁱⁿ²
(70.3 kg / cm ² ) Temperature: 110 ^о С СО / Н ₂ (molar) 1: 2 Ethylene oxide 10 g
Get the following experimental results (table. 6).

 These results show that although a limited amount of phosphoric acid, in particular such an amount that will provide an equivalent pH of about 1.6 or higher, is favorable for the catalyst system, for example, increases speed and / or selectivity, an excess amount of phosphoric acid can cause worsening of ethylene oxide hydroformylation reaction.

 PRI me R 52. Repeat example 50 with the exception that the catalyst precursor includes 2 mmol of triethanolamine and does not contain phosphoric acid. The molar concentration of triethanolamine is such that the equivalent pH of the aqueous solution of triethanolamine is about 10.0. The results of this experiment are as follows.

3-hydroxypropion selectivity- 3-hydroxypropion- formation rate
aldehyde and 1,3-propanediol, aldehyde and 1,3-propanediol,
moln mol / l / h
73 (74) ⁽¹⁾ 0.74 (0.76) ⁽¹⁾
(1) The value in parentheses is obtained from an exact duplicate experiment.

 These results indicate that triethanolamine promotes hydroformylation of ethylene oxide and that the experimental procedure used provides practically reproducible results. In particular, the presence of triethanolamine in the above concentration provides an increase in the rate of hydroformylation of ethylene oxide and an increase in selectivity in 3-hydroxypropionaldehyde and 1,3-propanediol.

EXAMPLES 53 and 54. Repeat example 2 twice with the exception that 2 mmoles of diphenol are included in the catalyst. The molar concentration of diphenol is such that the equivalent pH of the diphenol / water solution is about 5.4. In example 54, the hydroformylation reaction is carried out at 90 ^about C.

 The results of these tests are as follows (table. 7).

 These results indicate that certain concentrations of certain other substances, in particular diphenol at the above concentration, affect the selectivity and / or rate of formation of 3-hydroxypropionaldehyde and 1,3-propanediol during hydroformylation of ethylene oxide.

 In addition, lower hydroformylation temperatures may result in increased selectivity.

Example 55. The 3-hydroxypropionaldehyde from Example 47 was recovered, for example, by distillation and further processed as follows. 10.9 mmol of 3-hydroxypropionalaldehyde are added to 9 ml of water and transferred over a glass line to a 300 ml autoclave. 0.14 g of Raney 3100 nickel catalyst promoted by molybdenum in 30 ml of water is added to this autoclave. Set the pH to 7 with the addition of 3 N. sulfuric acid. The autoclave was sealed and pressurized to 1000 lbs / ⁱⁿ² (70.3 kg / cm ²⁾ at 22 ° ^C. The autoclave contents were heated to 105 ^{° C} and maintained at that temperature 2 hours. The temperature was raised to ^{160 °} C and held at this time after this temperature for 1 hour. The reactor was then cooled ^to 25 ° C and the contents analyzed. Found that 1,3-propanediol is obtained with a yield of 95%
PRI me R s 56-63. Example 50 is repeated several times with the exception that in each repeat, the catalyst precursor contains 2 mmoles of one of the various compounds, as described below, and does not contain phosphoric acid. The results of these experiments are shown below (table. 8).

 Each of the tested compounds in the applied concentrations provides an increase in the rate of hydroformylation of epoxides. In addition, such concentrations of these compounds provide increased selectivity for the target 3-hydroxypropionaldehyde and 1,3-propanediol.

Claims (15)

 1. The catalytic composition for hydroformylation of ethylene oxide, comprising a liquid medium, a rhodium-containing complex, a phosphorus-containing compound, an ionic component and a cation, characterized in that it contains an anionic rhodium-containing complex with a phosphite ligand with a molar ratio of ligand to rhodium 0.1-100.0, ionic a component connected by non-covalent bonds with an anionic rhodium-containing complex with a molar ratio of ionic component to rhodium of 0.1-10.0, and a cation different from hydrogen ion, with a molar ratio of cation to rhodium of 0.1-100.0.  2. The composition according to claim 1, characterized in that it contains a phosphite ligand with a molar ratio of ligand to rhodium 0.9 to 20.0.  3. The composition according to claim 1, characterized in that it contains an organo-containing cation comprising an element of group Va or VIa of the Periodic system.  4. The composition according to claim 1, characterized in that it further comprises a promoter component selected from the group comprising a nitrogen-containing compound, compounds containing hydroxyl, carboxyl groups, protonic acids and mixtures thereof, with a molar ratio of the promoting component to rhodium 0.1 -10.0. 5. The composition according to claim 4, characterized in that it contains a promoting component in such an amount that its molar concentration in the specified composition under the indicated hydroformylation conditions is such that the equivalent pH in an aqueous liquid at 22 ^° C containing only the same molar the concentration of the specified promoter component is in the range of about 1 to 12.  6. The composition according to claim 4, characterized in that it contains a promoting component selected from the group consisting of triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, diphenol, catechol, isophthalic, picoline, acetic, p-ethoxybenzoic acids, dimethylformamide, N-methylpyrrolidone and mixtures thereof.  7. A method of obtaining a catalytic composition for hydroformylation of ethylene oxide, comprising reacting in a liquid medium a source of rhodium, a source of a phosphorus-containing ligand and an ionic component in the presence of carbon monoxide and hydrogen, characterized in that the reaction is carried out under conditions effective to obtain an anionic rhodium-containing complex with a phosphite ligand under the molar ratio of the source of the ligand to the source of rhodium is 0.1-100.0 and the ionic component to rhodium is 0.1-100.0.  8. The method according to claim 7, characterized in that the ionic component comprises an anion that is sufficiently basic to deprotonize the hydride of the anionic rhodium-containing complex under conditions of hydroformylation of the epoxide.  9. The method according to claim 7, characterized in that the said interaction is carried out in the presence of a promoting component with a molar ratio of the promoting component to rhodium of 0.1-10.0.  10. The method according to claim 9, characterized in that the promoting component is selected from the group consisting of a nitrogen-containing compound, compounds containing hydroxyl, carboxyl groups, protonic acids and mixtures thereof.  11. The method according to claim 9, characterized in that the promoter component is selected from the group consisting of triethanolamine, 2,6-lutidine, benzimidazole, 2-methylimidazole, diphenol, catechol, isophthalic, picolinic, acetic, p-ethoxybenzoic acid, dimethylformamide , N-methylpyrrolidone and mixtures thereof.  12. The method according to claim 7, characterized in that the ionic component includes an organo-containing cation, which contains an element from group Va or VIa of the Periodic system.  13. A method of producing 1,3-propanediol and 3-hydroxypropionic aldehyde by reacting ethylene oxide, carbon monoxide and hydrogen in the presence of a catalytic composition comprising a rhodium-containing complex, a phosphorus-containing compound, at elevated temperature and pressure, characterized in that they use a catalytic composition containing an anionic a rhodium-containing complex with a phosphite ligand with a molar ratio of ligand to rhodium 0.1-100.0, an ionic component connected by non-covalent bonds with anionic rhodium-containing complex at a molar ratio of ionic component to rhodium of 0.1-10.0, and a cation other than a hydrogen ion, at a molar ratio of cation to rhodium of 0.1-100.0.  14. The method according to item 13, wherein the specified cation includes an organo-containing cation containing an element 43 of group Va or VIa of the Periodic system.  15. The method of obtaining 1,3-propanediol and 3-hydroxypropionic aldehyde by the interaction of ethylene oxide with carbon monoxide and hydrogen in the presence of a catalytic composition comprising a liquid medium, a rhodium-containing complex, a phosphorus-containing compound, an ionic complex and a cation at elevated temperature and pressure, characterized in that using a catalytic composition containing an anionic rhodium-containing complex with a phosphite ligand with a molar ratio of ligand to rhodium 0.1-100.0, an ionic component connected by non-covalent bonds with an anionic rhodium-containing complex with a molar ratio of the ion component to rhodium of 0.1-10.0 and a cation other than a hydrogen ion, with a molar ratio of cation to rhodium of 0.1-100.0.

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