TW391955B - Process for the preparation of acetals - Google Patents

Abstract

A process for the preparation of acetals by reacting allyl ethers with alcohols, wherein an allyl ether is reacted with an alcohol in the liquid phase in the presence of a homogeneous catalyst comprising an organometallic compound of the platinum metals, ruthenium, rhodium, palladium, platinum, osmium and/or iridium or in the presence of a heterogeneous catalyst which contains one or more of the elements chromium, molybdenum, tungsten, rhenium, ruthenium, cobalt, nickel, rhodium, iridium, osmium, palladium and/or platinum of the Periodic Table of Elements, under essentially anhydrous conditions.

Description

V. Description of the invention (A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This invention is about a method for preparing acetals through the reaction of propyl ether and alcohol. Awakening is widely used in king industry towels, For example, # as a starting material for preparing the corresponding aldehyde by hydrolyzing acetal 'or as a reagent for preparing acetal from aldehyde or ketone by converting the acetal reaction. In the preparation of perfume, acetal is based on a fragrance [Please refer to Riechstoffe, Aromen, Kosmetika u (197, 71). Acetals are usually obtained by reacting corresponding aldehydes or ketones with alcohols under acidic catalysts [Riechstoffe, Aromen, Kosmetika. 27 (1977), 71] In many cases, the relevant aldehydes cannot be obtained in the desired quantity from natural sources] or the prices of aldehydes from natural raw materials are so high that they cannot be widely used industrially for different purposes. Therefore, There is a need in the industry for a method for the economical production of chain shrinkage from petrochemical feedstocks. US-A 4 788 325 and Zhang's [J. Organomet Chem Lamp (1995) 31] describe the presence of allyl ethers and alcohols in hydrogen and carbon monoxide Next, use eight The reaction of carbonyl two words (C0 (CO) 8) as a catalyst can be used directly as a catalyst in the reaction or in a reaction mixture by a salt and carbon monoxide under pressure to perform a carbonation reaction. It is prepared in situ. Under the reaction conditions, octadecylcobalt is converted to cobalt tetracarbonylcobalt hydride (HCo (CO) 4) with hydrogen, which is a species with catalytic activity. The disadvantage of this method is that the used The carbohydrate compounds are relatively easy to volatilize, and when the product is gradually distilled, the P-peracetic acid will be discharged. Therefore, in further use, for example, as a fragrance agent, the acid must be self-contained in the expensive decobalization stage. Among them, cobalt carbonyl is released. Therefore, 'this method is not economical. US-A 4 658 069 is about allyl ether containing methylamido or carboxyl groups (please read the precautions on the back before filling this page)

Set the base of the high mountain base of V. Turn 4- This paper size applies to the Chinese National Standard (_ CMS) A4 size (210 X 297 mm) > It— ϋΒ Bn A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (2) In the first stage, the allyl ether is reacted with methanol at a ratio of two: Λ, and then the water obtained by the reaction is removed, and the first connection The allyl ether acetal obtained in the paragraph is converted into a saturated diacetal with the aid of dentified ruthenium alkanol. Other suitable catalysts are, ruthenium, iron, exemption, and deletion compounds. Because the foreign metal ... = 2 This method is not stable enough and it is easy to cause the relevant foreign metals to be deposited on the soil of the reaction container, which leads to the loss of precious metals. This method is not economical on an industrial scale. JP-A 25 i 14/1972 is a方法 In the presence of a catalyst, a method in which #propyl ether is reacted with an alkanol to prepare an acetal. The actual application of this application = 中 '1_methoxy · 2,7_octane system reacts with methanol, In a nitrogen atmosphere, u-dimethoxyoctyl- [ene is obtained via RuC13. This method also has poor catalyst stability. Disadvantages. The purpose of this article is to provide an economical method for the preparation of acetal ether acetal, but without the disadvantages of other technologies. It is found that this item prepares an acetal by reacting an alcohol with an acetal bond. Method, in which allyl ether and alcohol are in the liquid phase, in the presence of organometallic compounds of Group VIA and / or ¥ 111 group eight elements in the periodic table, in the presence of a catalyst, or In the presence of heterogeneous catalysts of via VIIA and / or group VIIIA metals in the periodic table or elements, the reaction is performed under substantially water conditions. The starting material used in the novel method of the present invention is allyl. Ether ri ^^^ \ 〇_r2 J where R1 is hydrogen or an organic group ', especially 1 to 17, preferably 1 to 10 carbon atoms, please read the precautions of the back first, and then there are no -5- Paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297 mm)

Cyclic 'straight or branched chain nicotyl. Examples of such hydrocarbon radicals are alkyl radicals, preferably C3_C | 7_alkenyl'aryl radicals whose double bonds are not conjugated to allyl, such as phenyl or fluorenyl, c3-c8: cycloalkyl, alkylaryl and Aralkyl. Depending on their size, this: The hydrocarbyl group may be substituted with 1 to 3 substituents which are inert under the reaction conditions, such as an ester or alkoxy or aryloxy group. R1 is preferably a linear, branched or cyclic alkyl group. R2 in the allyl ether of formula I is an organic group having 1 to 20, preferably 1 to 10 carbon atoms. R2 is preferably a hydrocarbon group, such as a linear or branched c_c20-alkyl group, preferably CrC | O_alkyl group, C3_C8_cycloalkyl group, c3_c ^ alkenyl group, car ^ q-Cf alkyl group, or crc8_ Cycloalkenyl (the double bond of the alkenyl is preferably not present at the alpha position of the oxygen atom of the allyl ether) '. 64. -Aryl, such as phenyl or fluorenyl, or C7-Cn-aralkyl or alkaryl. R2 is preferably bonded to the oxygen atom of the allyl ether via a carbon atom of the first or second order. Particularly preferred R2 is a linear or branched alkyl or alkenyl group. Depending on its size, the organic group R2 can carry i or 2 in the reaction: the substituent is inert under the component, such as Ci_c 丨. _Alkoxy. Depending on its size, R2 can also be used! Or 2 hydroxy substituted. However, M is preferably free of other substituents. "Dim & is used as the starting material in the present invention. The propyl ether I is listed below, but for the purpose of illustration only: allyl methyl ether 'allyl ethyl ether, propyl propyl n-propyl ether , Allyl n-butyl ether, diallyl ether, (but-2-enyl) methyl ether, (but-2-enyl) ethyl ether, (but_2_fluorenyl) n-propyl ether , (But_2_alkenyl) n-butyl ether, bis (but_2_alkenyl) ether, oct'7_dienyl methyl ether 'oct-2,7-dienyl n-butyl ether, di (Oct'7_dienyl) ether and butoxydodecyl-2,7,11-triene. In the alcohol r3Oh 11 used in the present invention for the production of acetals in accordance with equation VII.

(Please read the notes on the back before filling out this page) 1Γ Consumption Cooperation by Employees of the Central Bureau of Standards, Ministry of Economic Affairs -6-

A7 B7 V. Description of the invention (4 OR3

(1) III ⑽ + R3〇H contact ^

1 II where it is speculated that the reaction is via associated ether! Isomerization to intermediates ... and the occurrence of the substituent R3 may be different from that contained in the allyl ether used. The primary or secondary alcohol R3OH is preferably used, and the primary alcohol R3OH is particularly preferably used. The tertiary alcohol R3oh can also be used, but due to the bulkiness of the substituent rule 2, steric hindrance may occur during the reaction. Therefore, the alcohol R 0H is preferred because R 2 does not cause steric hindrance. Particularly preferred is the use of an aliphatic CrC4-alcohol as R30h, especially methanol, ethanol, n-propanol, isobutanol and n-butanol. The alcohol R30h used may of course also be a polyhydric alcohol, such as ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1 > butanediol or fluorene, hexanediol. If R2 contains a hydroxyl radical, it can be reacted intra- or intermolecularly with a double bond to form a ring or propionyl acetal, that is, the hydroxyl group present in the substituent R2 is used as the alcohol r3OH. In terms of sentiment. Consumption cooperation with employees of the Central Bureau of Standards of the Ministry of Economic Affairs prints many organometallic compounds of transition metal elements, especially Group VIA and VIIIA elements in the Periodic Table of the Elements, preferably molybdenum, iron, nickel, nickel, especially platinum metal ruthenium , Germanium, palladium, platinum, osmium, and iridium, particularly preferably ruthenium, osmium, iridium, or hungry organometallic compounds' can be used as acetalized allyl groups in the present invention to obtain homogeneous contact of acetal III Media. For the application of the present invention, organometallic compounds should be understood to refer to complexes of transition metals and containing ligands such as _'antimony, arsenic, nitrogen, sulfur, and / or oxygen, and via free electricity. Applicable to China National Standard (CNS) A4g (210X297 mm)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs on covalent coordination with transition metal coordination. For example, Λ is similar to organic amine ligands, organic free ligands, and complex ligands, such as acetone and acetone. Two, such as dimethyl difat, bran, or rib, diuretic, urea or thiourea, 8 via Kikulin 'single or multi-ligand', especially di-ligand Gite and organic phosphite ligands, organic amidines and organic amidine ligands, and aromatic nitrogen-containing ligands ((-N = CC = N-) structure is the reason for making it a complexing agent) For example, 2,2 bite or i, 10-morphine, Lin, and ligands such as tertiary pyridine derived from these parent materials through substitution. These complexes can exist as neutral complexes, or they can be charged and can form salts with anions. On the other hand, these simple transition metals and simple salts of, for example, a few acids, carbonic acid, or hydrogenic acid, which do not contain any of the above-mentioned organic ligands, are not considered as compounds used for the purpose of the present invention. Similarly, carboxylates, cyano, or carbonyl complexes of transition metals, such as cobalt dioctacarbonyl (c0 (c0) s) or cobalt tetrahydrocarbon hydride (HCo (CO) 4), do not include the above Organic ligands. On the other hand, a complex of a metal with the above-mentioned organic ligand_ which additionally contains a carboxylic acid salt, an alcoholate, a cyanide, a carbonate or a carbonyl ligand bound in the form of a complex, or contains a carboxylic acid The anions of salts, alcoholates, cyanides, carbonates or sulfates as transition metal positively charged organometallic complexes are included within the definition of & metal compounds. The ligand used may be a single ligand or a multi-ligand, such as a di-ligand phosphine ligand. Suitable phosphine ligands are, for example, trialkylphosphine, triarylphosphine, alkyldiarylphosphine ' aryldialkylphosphine, aryldiphosphine, alkyldipentyl, and aryldiphosphine. The alkyl-supported phosphine ligand may contain the same or different CVC2. -Fluorenyl, preferably crcs_alkyl, or cycloalkyl. Phosphine ligands carrying aryl groups may contain the same or different C (5_C12_aryl groups, especially -8-This paper size applies to China National Standard (CNS) A4 specifications (2 丨 0X297 mm) (Please read first (Notes on the back please fill out this I)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (6) Phenyl or naphthyl, and diphenyl. Other phosphine ligands that can be used to misinterpret VIA or VIIIA catenins are heterocyclic aliphatic groups such as pyrrolidine, imidazoline, hexahydropyridine, morpholine, oxazoline, hexahydropyridine Hydrazone or triazolyl 'or heteroaryl' such as pyrrole, imidazole, oxazole, pyridine, pyridine, perylene, pyrimidine, pyrazole, pyrenyl, or pyridazinyl, and other alkyl or aryl phosphines Ligand. The alkyl or aryl group of the ligand may be unsubstituted or may carry a substituent that is inert under the reaction conditions, such as C, C4_ @ oxy or di-crC4_alkylamino, crc6_alkyl , Nitro, cyano or sulfonate. Examples of suitable phosphonate ligands are, in particular, triphenylphosphine trisulfonate (TPPTS) and triphenylphosphine monosulfonate (TppMS) (Angew.

Chem. 105 (1993), 1588). In principle, this is equivalent to the applicability of the ligands used to misinterpret the group VIA or νΠΙΑ element in the present invention. However, for cost reasons, it is preferable to use a ligand that can be prepared in a simple manner. Some of these ligands are by way of example only: trimethylphosphine'diethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, trioctylphosphine'tridecyl Phosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, xylylphosphine, cyclohexyldiphenylphosphine, tetraphenyldiphosphine, 2-bis (diphenylphosphino) ethane , Tetramethyldiphosphinomethane, tetraethyldiphosphinomethane, 1,3-bis (diphenylphosphino) propane, 4-bis (diphenylphosphino) butane, tetra-secondary Butyl diphosphinomethane, L2-bis (dimethylphosphino) ethane, 152_bis (diethylphosphino) ethane, 1; 2-bis (dipropylphosphino) ethane, 丨, 2_bis (diisopropylphosphino) ethane '1,2-bis (dibutylphosphino) ethane, 1,2, bis (di-secondary butylphosphino) ethane, 1, 1_bis (dicyclohexylphosphino) methane, 2_bis (dicyclohexylphosphino) ethane, 1,4-bis (dicyclohexylphosphino) butane and EP-Α 9- paper size Applicable to China National Standard (CNS) Α4 specification (210x297 male thin) ..----------- (Please read the notes on the back first (Fill in this page again) Order A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs _ V. Description of the invention (7) 279 018, EP-A 311 619, W90 / 06810 and EP-A 71 281 Phosphine ligand. Preferred phosphine ligands other than triphenylpentene (condensation is PPh3) are via a cvc4-alkylene bond and a phosphine ligand having the following two formulae:

A \ / A P- (CH2) η-Ρ / \

A A where η is an integer of 1 to 4, and the groups A are the same or different q-C ^ -alkyl or Cr or C6-cycloalkyl '. Some typical examples have been mentioned above. In addition to the methods described in the aforementioned patent applications, alkyl- or arylphosphine ligands can be prepared using known methods, such as Houben-Weyl,

Methoden der Organischen Che.mie, Book XII / 1, 4th edition, pages 17-65 and 18.2-186 'Thieme, Stuttgart, 1963, and Book E 1, 4th edition, pages 106-199, Thieme , Stuttgart, 1982. Suitable phosphate ligands are, for example, trialkyl phosphates, alkyl diaryl phosphates' triaryl phosphates, alkyl. Diphosphites, aryl diphosphites, and pit aryl diimides Phosphate. Carbyl-loaded phosphate ligands may contain the same or different cvc !. -Alkyl, preferably crc6-alkyl, or cyclopityl. The aryl group-bearing acid salt ligand may contain the same or different cvCf aryl's, especially phenyl or theophyl, and diphenyl or diphenyl. Other phosphate ligands that can be used to make the transition metal are heterocyclic aliphatic groups such as pyrrolidine, imidazolidine, hexahydropyridine, morpholine, pyrimidine, hexahydropyridine or tripyridyl 'Or heteroaryl, such as pyrrole, imidazole, vomiting,' ^ 丨 p 木 'pibidian, pkui plin, p dense bite, ρ than ρ sitting ,? Bi wells, or 'daphnosyl,' are ligands for other alkyl or aryl groups. Alkyl or aryl of phosphate ligands -10- This paper size applies to 6 National Standards (CNS) 8 4 Lin (210X297) Chu ':-~ 丨 -------- Sound! (Please read the precautions on the back before filling out this page) Order. FgE§ Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (8) The base may be unsubstituted or may be contained in the reaction Substituents that are inert under conditions such as crcv alkoxy, di-crc4-fluorenylamino, Crc6-alkyl, hydroxy, acyl, cyano, or transacid. Phosphonate substituted phosphate complexes and their complexes are generally water-soluble. Suitable phosphate ligands are 'e.g. dimethylscale acid. Salt, diethylscale acid salt, tripropylscale acid salt, triisopropyl phosphate, tributyl phosphate, tricyclopentyl phosphate Salt, tricyclohexyl phosphate 'triphenyl phosphate and EP-A 472 071, EP-A 213 639, EP-A 214 622, DE-A 2 733 796, EP-A 2261, EP-A 2821, EP -A 9115, EP-A 155 508, EP-A 353 770, US-A 4 318 845, US-A 4 204 997 and US_A 4 362 830 as described in the mono- and bisphosphite ligands. In addition to phosphine or phosphate ligands, alkyl- or aryl-substituted or fused 2,2'-dipyridines or or 1,10-morpholine derivatives-containing 2,2, -dipyridines Or 1,10-morpholine ligands have (_N = c_C = N-) groups that have ligand-forming properties, such as 2,2'-dioxoline, 4,7-diphenyl-pyrene, ι〇- Phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-morphine, 4,5-diazopyridine's dipyrrole [3,2-a: 2,3,- c] Phenazine, 2,2 ', 6 1,2 "-terpyridine, 2,2, -dipyridine or 1,10-morpholine ligands can also be used in the method of the present invention. These compounds Some of the bases can be commercially available, such as 2,2'-dipyridine or 1,10-morpholine, and others can be prepared by the method described in Synthesis 1 (1976) or Aust_ J. Chem_ 23 (1970), 1023 These complexes of Group VIA or Group VIIIA elements which can be used in the present invention can be prepared in the mixture in situ, or they can be formed beforehand and then added to the reaction mixture. As far as the complexes are concerned, the manufacturing conditions In other words, compounds of Group VIA or VIIIA elements, such as their halides, are preferably chlorinated. , Bromide or iodide, nitrate, cyanide or sulfate -11-- Precautions This paper scales applicable Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the back of the idle and then fill this page]

Printed by A7 _B7 _ of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (9) or 'especially preferred is a complex of these metals, such as acetamacetate', and several bases. Substances or bromide smoke complexes, such as ethene or butadiene complexes, are fed into the reaction mixture together with related ligands, so the complexes formed in the reaction complexes can be used in the present invention Thing. Generally speaking, the molar ratio of the relevant ligands here is based on 1 to 200 of Group VIA or Group VIIIA elements, preferably 1 to 50, particularly preferably i to! 〇. Among the above-mentioned organometallic compounds of transition metals, there are platinum metal carboxyl complexes containing phosphorus-containing ligands, especially phosphine ligands, such as HRh (PPh3) 3 (CO) 'IrCl (CO) (PPh3) 3 , [Ir (cyclooctadienyl) pph3) 2] PF6 'HRuCl (PPh3) 3 (CO), HRu (CO) (CH3COO) (PPh3) 2, H2Ru (CO) (PPh3) 3, HRuCl (CO) (Hexyldiphenylphosphine) 3, ruh2 (pph3) 4, RuCl2 (CO) 2 (PPh3) 3 or RuH (CO) (C9H19CO〇) (pph3) 2, where

CgH ^ COO is a capric acid anion 'and is particularly preferred as a homogeneous catalyst in the method of the present invention. Among these homogeneous catalysts, halogen-free complexes are preferred in sequence, for example, conjugate bases containing 0-H-acidic organic compounds, and complexes '0-H-acidic' as ligands. An organic compound refers to a compound that is acidic in an aqueous solution, such as a monocarboxylic acid, a monosulfonic acid, or a non-binding phenol. Cj-C2 which is derived from mono-acid acid is preferred. -Carbonic acid anions, such as acetate, propionate, butyrate, isobutyrate, valerate, pivalate, hexanoate, sulphonic acid 'Sinu salt' 2-ethylhexyl salt '2 -Propylvalerate, caprate, laurate 'myristic acid' palm salt, stearates, oleates, benzoates, acid salts, alkyl benzoates, phosphonates and alkanes A naphthonate anion, or a non-coupled phenate or sulfonate anion, can be advantageously used as a 1 ^ ligand. Μ can be advantageously used as a ligand in organic transition metal compounds. -12- This paper scale is applicable to China National Standard (CNS) A4 specifications (210X297); (I read the precautions on the back before filling this page) 4 Order A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The phenate of invention description (1) is, for example, a phenate substituted on an aromatic nucleus with a substituent that is inert under the reaction conditions, and osmic acid Salt anion and phenate and benzoate anion, = ^ alkyl substituted, preferably CrCiG_ alkyl substituted phenate or naphthate, such as methyl phenate, nonyl phenate, 2, 6-di-tertiary butyl phenate or 2,6-di-tertiary butyl-4-methyl phenate anion. Sulfonate ligand systems which can be advantageously used for the purpose of the present invention, for example, alkanoates such as methane sulfonate, octane sulfonate, dodecyl sulfonate, octadecanesulfonic acid Salt or trifluoromethanesulfonate anion, or arylsulfonate, such as tosylate anion. The preparation of the homogeneous catalyst containing the ligand derived from the acidic organic compound and the homogeneous catalyst which can be used in the present invention is a typical example of the above-mentioned ruthenium complex as a similar complex of other transition metals. These are briefly described as follows: The complexes of the acid salt ligands can be obtained, for example, from available RuH2 (PPh3) 3 (CO) as starting material according to Uttley et al. In "Inorganic Synthesis", Book XVII (1977), page 125 It is similar to Robinson et al. J_Chem. Soc_, Dalton Trans. (1973) 1912, Frediani et al., By reacting with the corresponding acid reaction, ibid. (1990) p. 165, ibid. (1990) p. 1705 , Ibid. (1990), p. 3663, and the method proposed by Frediani et al., J Organomet Chem. 454, C17-C19 (1993). Corresponding complexes containing phenate ligands can be made similarly H2Ru (CO) (PPh3) 3 can be obtained by reacting with related phenols. The complexes containing a continuous acid salt ligand can be obtained by the method described in US-A 4 892 955, for example. For example, the method described in Uttley et al. Inorganic Synthesis Book XV (1974), 45 It is obtained by the reaction between RuC13 and osmic acid. The above catalysts can be added to the same reaction batch or-especially if it contains -13 paper sizes that are applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (please listen first) Read the notes on the back and fill in this page again} Ding Dong. A7 B7 Consumption Cooperation with Employees of the Central Standards Bureau of the Ministry of Economic Affairs 衽 Printing 5. Description of Invention (Ή) Homogeneous catalysts of carboxylate or phenate ligands_ 在 反应The mixture is prepared in situ by the reaction of RuH2 (PPh3) 3 (CO) with the relevant phenol. In addition, 'Hydride and carbonyl groups are included because they are derived from complexes without hydride or carbonyl ligands. Ligand complexes can be generated in situ in the reaction mixture by forced mixing in molecular hydrogen and / or carbon monoxide. These are modified with carboxylate, sulfonate or phenate ligands and additionally The organic transition metal compounds containing phosphorus-containing ligands, especially phosphine or phosphate ligands, and preferably carbonyl ligands, if necessary, are particularly preferred because of their high activity. And selectivity and high stability, so The characteristics of long-term operation are the homogeneous catalysts selected by the method of the present invention as acetalization catalysts. The advantageous properties of these homogeneous catalysts can additionally be formed by the complexation of the transition metal carboxylate or phenate in the relevant transition metal. In the presence of a greater amount of the relevant acidic compound in stoichiometry, the acidification is improved in such a way that the related acidic compound in the free state is balanced with the organic transition metal compound as a homogeneous catalyst. For this purpose, the acidic compound used is advantageously the same as the transition metal compound bonded to the organic transition metal compound, but other acidic organic compounds are added in the same manner. In such procedures, acid organic compounds are generally used in an amount of 1: 1 molar ratio based on the organic transition metal compound as a homogeneous catalyst. Although it is not necessary to add hydrogen to the reaction mixture, it is necessary to add a small amount of hydrogen, if necessary, with a small amount of carbon monoxide. When a homogeneous catalyst containing a slave group is used, these homogeneous catalysts can be made. Life time is extended. In practice, syngas can be used for this purpose. It should be noted here that due to the reaction temperature used and the partial pressure used, -14- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)-* i »r» —Mi nnn HB m rn 4— = ttRνϋ tK «.mc Please read the notes on the back before filling out this page} Order I-A 7 _; _______ B7_. V. Description of the invention (12) Go, 氲 and / or carbon monoxide and the reaction mixture In the presence of a homogeneous catalyst, a transition metal complex reaction exists. Due to its multiple catalytically active organometallic transition metal complexes with different numbers of hydride groups and carbonyl ligands, it may be possible to reach each other in the reaction mixture under these conditions. balance. In order to improve the activity, selectivity and stability of homogeneous catalysts, especially homogeneous catalysts including phosphorus-containing ligands, phosphine or phosphate is usually added 2 to 100 times, preferably 2 to 20 Times, particularly preferably 2 to 10 times the molar number of phosphine or phosphate complexes of transition metals. If the transition metal complex as a homogeneous catalyst is prepared in situ in the reaction mixture, it is advantageous to add a correspondingly excessive excess of phosphine or phosphate ligands based on the relevant transition metal. The transition metal catalyst uniformly dissolved in the reaction medium is usually used in an amount of 1 to 1, preferably 1 to 1 mole% based on the allyl acid_I 0.001 in the feed soil reactor. It is obvious to those skilled in this art that the addition of homogeneous catalyst depends on the catalytic activity of the homogeneous catalyst in each case. Depending on the type of homogeneous catalyst used, a larger or smaller amount of catalyst can therefore also be advantageously added to the reaction mixture. The optimum amount of homogeneous catalyst used in each case is advantageously determined by preliminary experiments. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The acetalization reaction with the above-mentioned homogeneous catalyst can be performed in batches, for example, in a mixing tank, Or continuous, for example, in a ring reactor or a stirred tank stepped hair dryer, the temperature is generally 20 to 200 t, preferably 60 to 180 c 'particularly 80 to 160 ° C, The pressure is generally 1 to 100, preferably i to 60 bar. The acetalization reaction can be carried out in a solvent such as an aliphatic or aromatic hydrocarbon such as toluene, benzene or cyclohexane, an ether such as dibutyl ether 'tetrahydrofuran or dioxane, or a liquid low molecular weight Polyalkanediols, halogenated aliphatic or aromatic hydrocarbons, such as chloroform, dichloromethane, chlorobenzene or dichloro-15- ^: What is used for? ΐNational Standards (CNS) A7 A7 Printed by the Consumer Cooperatives of the 夬 Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) Stupid, thallium or thorium, such as dimethyl sulfoxide or pentasulfoxane. The acetalization reaction of the present invention is carried out under essentially anhydrous conditions, i.e., in the absence of a technically effective amount of water, because the presence of water adversely affects the results of the chemical reaction. Obviously, trace water has no measurable effect on yield, and this effect is tolerated. The method of the present invention can be performed without using these conventional solvents. The isodanization and acetalization reactions in which ether 1 is used to obtain m can also be performed in a phosphine melt. This process can be advantageous in the case of phosphine-containing homogeneous catalysts. Generally speaking, in principle, the phosphine of the agent can be freely selected in principle, but the choice of tritium in the solution is more important as a ligand for the transition metal complex used as a homogeneous catalyst. The range of the amount of alcohol R3OHn added is wide. The acetal formation can also be exceeded. Generally, the alcohol R30Hi1 is added based on the molar ratio of u-propyl ether w1: im00: 1 used, preferably 1: 1 to 10: 1.1 to 5.1. Take fenprofen 丨 alcohol R3〇: H II usually does not have

耵 Reverse search, 'mouth fruit reached an adverse effect, but the beneficial amount of alcohol R30H I is as described above. After taking tit: beam two, the product is usually subjected to distillation, and the homogeneous catalyst can return the residue to A, which can be reused if necessary. If it is assumed that a catalyst is used, it is advantageous to add the reaction mixture in the form of distillate, tantalum, and a solvent whose boiling point is formed by the reaction to form acetal III. If the homogeneous contact used has thermal and chemical stability, the step of adding a little solvent can be omitted, and the homogeneous catalyst can be refluxed to the reaction. -16 ^ 一 -__ 本 ' The Zhang scale is applicable to the Chinese National Standard (CNS) A4 secret (2! GX297 round) (Please read the precautions on the back before filling this page) Dingquan A7 ----: ---- B7 V. Description of the invention ( 14) For example in a triphenylphosphine melt. In another specific embodiment of the method of the present invention, the isomerization and lightening reaction of allyl ether I to acetal III is performed using a homogeneous catalyst, and the method is advantageously performed in the liquid phase. . It was found that, surprisingly, a conventional heterogeneous chlorination catalyst which is substantially insoluble in the reaction medium can be used as a catalyst for converting propyl ether to acetal II. Among these hydrogenation catalysts, it is preferable to include one or more elements of Group IA, VIA, VIIA, or VIIIA in the periodic table, and if necessary, the same or more elements of Group VA, especially It is a catalyst for chromium, molybdenum, tungsten, chain, ruthenium, cobalt, nickel, rhodium 'iridium, palladium and platinum, and iron and / or copper if necessary. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) In the method of the present invention, for example, the precipitated catalyst 7 can be used as a heterogeneous catalyst. These catalysts can be obtained from their salt solutions, in particular from their nitrate and / or phthaloyl salt solutions, by adding alkali and / or alkaline earth metal hydroxides and / or carbonate solutions, such as instantaneous soluble hydroxide Compounds, hydrated oxides, basic salts or carbonates to precipitate their catalytically active compounds, and then the resulting foot precipitate is dried, and then converted to calcination, usually at a temperature of 300-700 (rc, particularly ° C). Relevant oxides from oxidizing compounds that are reduced to relevant metal friends / or to low oxidation states, for example, by reducing agents, such as hydrogen or hydrogen-containing gases, usually at 50-700 t: especially at 100-400 ° C. , Mixed oxides and / or mixed polyvalent oxides, and then converted into the actual catalytically active form. Usually the reduction reaction continues until water no longer forms. When the precipitated catalyst containing the carrier is produced, the catalytically active group The precipitation of the components can be carried out in the presence of the relevant carrier. However, the catalytically active components can also be advantageously precipitated together with the carrier from the relevant salt solution. In this case, Example -17- this paper scale applies to China Standards (CNS) (210X297 Gongchu) A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (15) If the catalytically active components are precipitated in a water glass solution. Contains catalytically active metals or is deposited on a carrier Catalysts of metal compounds are preferably used in the method of the present invention. In addition to the above-mentioned precipitated catalysts that also include carriers other than catalytically active catalysts, the supported catalysts and catalysts are generally supported. Application by impregnation on the carrier-suitable for the method of the invention. The method of applying the catalytically active catalyst to the carrier is generally not decisive and can be carried out in a variety of ways. The catalytically active metal can be, for example, related to Solution or suspension of salts or oxides of the elements on these supports' dried and via a reducing agent, preferably hydrazine, to reduce the metal compound to the relevant metal or oxidized compound in a low oxidation state. A catalytically active catalyst is placed on the support Another possible method is to quickly decompose salts, such as nitrate solutions, or complex compounds that decompose rapidly when heated. For example, the carbonyl or carbonyl complex of the catalytically active metal is impregnated with the support, and the support impregnated in this manner is heated to 300 to 60 ° C. to thermally decompose the absorbed metal compound. The thermal decomposition is better It is carried out under an atmosphere of an inert gas. A suitable inert gas is' for example nitrogen, carbon dioxide, hydrogen or an inert gas. In addition, the catalytically active metal can be deposited on the catalyst carrier by a vapor deposition method or by a flame spray method. These The content of catalytically active metals in supported catalysts is not critical in principle, as long as the method of the present invention can be successfully carried out. It will be apparent to those skilled in the art that these supported catalysts contain a relatively high amount of Catalytically active metals make the space-time yield higher than those with lower and lower catalytically active metals content. However, loading catalysts containing f% of catalytically active metals based on the total weight of the catalyst are preferably from 0 to 80, preferably from 0.5 to 30 weight percent. Media. Because these mentioned -18- this paper size is applicable to China National Standard (CNS) 8 4 specifications (_ΙΓ ^ × 297 common sewing) (Please read the precautions on the back before filling this page) Order ... Description of the invention (16 A7 B7 Printed content of the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, the total weight of the catalyst-including the carrier-is based on the base, but different carriers have very different degrees and surfaces. However, it is also possible to use smaller or larger amounts without adversely affecting the results of the method of the present invention. ^ Several catalytically active metals can also be deposited on separate supports. Second, the catalytically active metals can be borrowed The method is applied to a carrier ± by methods such as DE_A 2 519 8i7, Ep_A Takikawa, and EP-A 285 420. In the catalysts of the above-mentioned announcement, the catalytically active metals are taught to obtain complexes from the salts of the above-mentioned metals and / Reduction-derived alloys exist in which the salt or complex is deposited on the support by, for example, impregnation. In general, aluminum or titanium oxides, zirconia, silica, diatomaceous earth, silica gel, Alumina, such as montmorillonite, silicic acid Salts, such as magnesium silicate or aluminum silicate, zeolites, such as ZSM-5 or ZSM-10 zeolites, and activated carbon can be used as carriers. The preferred carriers are alumina, titania, zirconia, and activated carbon. Of course, it is also possible to use A mixture of different carriers is used as a carrier for the catalyst of the present invention. Examples of heterogeneous catalysts that perform only the acidification reaction are the following catalysts: platinum oxide, palladium / alumina, palladium / silica, palladium / barium sulfate , Palladium / zirconia, rhodium / activated carbon, rhodium / alumina, ruthenium / silica or ruthenium / activated carbon, nickel / silica / crushed stone 'Record / Oxide Ming' carbonyl iron powder, chain handle / active Carbon, Chain | White / Activity So 'Mixed Oxide-Oxidation Miscellaneous Mixture, Saturated / Activated Carbon ... / Molybdenum oxide / silicon oxide / alumina catalyst, # bar / activated carbon catalyst partially exposed to selenium or toxicity, and according to DE_a 3 932 332, US-A 3 445 'EP-A 44444, EP-A 147 219, DE-A 3 904 083, DE-: 321 1CU 'eP-A 415 202, DE-A 2 366 264, and EP-A 100 406 in contact with lead 449 -A 2 (Please read the note on the back first Please fill in this page again) X. 19- This paper size applies Chinese National Standard (CNS) A4 specification (21〇297 thin) A7

Silicone's Consumer Co-operative Society of the Silicon Economics Central Standards Bureau printed Siyi 1 to 391955 on average. V. Invention Description (17). Includes Brewster and / or Lewis Acid Center for use in the method of the present invention. Lice-activating catalysts can also be exemplified by catalytically active metal easy acid centers, if they are reduced to the relevant metals in the catalyst: Chlorine. This example is not completely as infective when activated. Copper. This :, two =: succinate catalysts, for example, can be placed on the carrier through the use of 5 ^ sigma or test center, the sentence media contains Bronst or Zhenghe = center of the example It is an oxide inscription, a dioxin, an osparic acid; an oxide inscription "", a mixed magnesium / oxidized inscription and a live: carbon. Includes ^ TA ^ θ-standing A, νϊ 'Vn and / in the periodic table Or element VIII, especially the subgroups νπ and VTTT in the periodic table. T Special or prepared on the carrier of the Lewis acid = Bei Zai is regarded as the load catalyst of Brenz ,, +, and ". It is best used in the present invention: Litian is used as a JL catalyst. The particularly advantageous catalyst is, For example, ruthenium on aluminum, ruthenium on silica, zirconia ^, zirconia, oxidizing inscription = free on the stone, emulsified zirconium on zirconium, on sparse acid steel Exemptions and exemptions on activated carbon catalysts that are partially or lead poisoned. Bronister or Lewis acid components, such as stagnation, oxidizing or stone, phosphoric acid or sulfuric acid 'can be added per se without these Bronister or The catalyst of the road center is usually added in an amount of 0.05 to 0.5, preferably 0 to 0.4% by weight based on the weight of the catalyst used. It is also commonly used for allyl. The ether 丨 converted to acetal m is a heterogeneous catalyst containing heterogeneous organometallic complexes selected from the group VIA and VIIIA transition metals in the periodic table of the elements, such as non-20- This paper size applies to China National Standard (CNS) A4 specifications (2I0X297 mm (please read the precautions on the back before filling in this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 391955 V. Description of the invention (18) Phase catalyst, this compound can be used for homogeneous catalysis in this processing stage. These polymeric matrices can be resins, such as styrene / divinylbenzene resin or phenol / formaldehyde resin, acetophenone / diethylfluorenylbenzene resin or phenol / formaldehyde resin, which are used to intermix the relevant components of transition metal elements. The positional groups are preferably covalently bonded, and the ligands sequentially form complexes with related transition metals, thus rendering these related transition metals virtually inactive. The complexes of these heterogeneous bonding polymers of group VIA or VIIIA elements, especially the complexes of palladium and nickel complexes, can be performed by, for example, the method of Zhuangyu et al. (Reactive Polymer 2_ (1988) 249) or according to Wang et al. (Jorg. Chem. This (1994), 5358). The immobilized phosphine complexes of Group VIA and Group VIIIA elements can be obtained, for example, by Hartley, Adv. Organomet. Chem. (1977). 189, F.R. Hartley, supported metal complexes, Riedel, Dordrecht 1985 'K · Smith, Solid Supports and Catalysts for Organic Synthesis' Ellis Horwood, Prentice Hall, NY 1992 > CH Pittman, Polymers Supported by Reactions in Organic Synthesis, p. 249, Wiley, Chichester 1980 and CH Pittmann J. Am. Chem. Soc M (1976), 5407 and Ann. NY Acad. Sci. 245 (1977), 15. The advantage of using such heterogeneous catalysts is, in particular, the easier and gentler separation of the catalyst from the reaction products. The catalyst may be placed in a fixed bed through which the reaction mixture flows or may be suspended in the reaction mixture and mechanically separated after the reaction is completed. Heterogeneous catalysts can be used in suspension in a liquid reaction medium or, preferably, in one or more fixed beds. When a heterogeneous catalyst suspended in a liquid reaction medium is used, the method can be performed in, for example, a stirred tank or a ring reactor. When using a heterogeneous catalyst placed in a fixed bed, the reaction mixture -21-This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

IJmlglMileitma .. · :: .1 391 ^ 55 A7 V. Description of the Invention (19 The printing of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs usually prints through a fixed catalyst bed through a j-phase or liquid or liquid bed process bed. General In terms of catalysts, the liquid mixture is loaded with a liquid mixture at a space velocity of 0.001 to 2, preferably 0.001 to .5 'per litre of catalyst per hour, and 0.05 to 100 kg of reaction mixture. When using non- In the case of a homogeneous catalyst, the reaction can be carried out in the presence or absence of a solvent. The solvent used can be the same as the solvent that can be used to carry out the reaction in the presence of a homogeneous catalyst. The amount of alcohol R3OHn is added in a wide range. The amount of moire required to form acetal III can also be exceeded if necessary. In general, the alcohol R3OH II is based on II /, based on the allyl ether used in the reaction. i:] to 100. 1 ', preferably from 1: 1 to 10: 1, especially from 1: 1 to 5: 1. A very excess alcohol R3OH based on allyl ether I is usually not available. The reaction results have an adverse effect, but the beneficial amount of alcohol R30H π is as described. On liquid phase heterogeneous catalysts The isomerization and acetalization of the allyl ether to acetal is usually at "to%. ^, Preferably 50 to 280, more preferably 80 to 250 c, and usually at i to 1 〇〇, preferably i to 50, especially at a pressure of 2 to 10 bar. The liquid reaction extract from the reaction stage is usually distilled in a manner similar to that described above for the subsequent stages with a catalyst. When using non- In the case of homogeneous catalysts, the recycling of the catalyst is slightly as if it is regarded as an advantage in a special environment when using homogeneous catalysts, and of course it can be omitted. The acetal can be started from propyl ether through the method of the present invention, and Good rate and selectivity. In particular, the catalyst used in the method of the present invention is characterized by good separability of its reaction products and good stability, which can overcome the shortcomings of the prior art. The examples are all on the production site from the -22 (please read the precautions on the back before filling this page)

391955 A7 B7 5. Description of the invention (20) Example 1 0.022 g of catalyst HRuCl (CO) (PPh3) 3, 0.03 1 g of triphenylphosphine, 0.005 g of capric acid, 3-18 g (24_8) Millimoles) n-butanol and 1_83 grams (24.8 Emory) of 1-butoxybutane_2_ dilute. After 16 hours of reaction at i60 ° C under autogenous pressure, the reaction mixture was analyzed via calibrated gas chromatography. A conversion of 85% results in the formation of 1,1-dibutoxybutane with a selectivity of 85.1% and 1-butoxybutene with a selectivity of 10.1%. Example 2 A glass autoclave was charged with 0.01 g of heterogeneous catalyst palladium / activated carbon (10 wt% Pd), 3.0 g (24 mmol) of 1-butoxybut-2-ene and 1.73 g (24 mmol) n-butanol. After 16 hours of reaction at 150 ° C under hydrogen atmosphere (1 bar), the reaction mixture was analyzed by calibrated gas chromatography. A conversion of 21% 'forms U-dibutoxybutane with a selectivity of 42%, dibutyl ether with a selectivity of 25%, and 1-butoxybut small olefin with a selectivity of 22%. (Please read the notes on the back before filling this page)

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Claims (1)

391955 Fasting Amendment 丨 4, the scope of application for patents 1. 7 methods for preparing acetals by the reaction of alcohols and allyl ethers, whose M is in the liquid phase, including metals such as Ming, Shu, Lu, Wu, Chu, Lu ― And / or the presence of a homogeneous catalyst for an iridium organometallic compound i containing one or more elements of the periodic table, I, molybdenum, tungsten, chain, ruthenium II:., Rhodium, iridium, starvation, palladium and / Or heterogeneous catalysts of element or element exist in the condition that they are essentially water-free to react. 2. ^ The method according to item "Scope of the Patent," in which the homogeneous catalyst used for the brand is platinum-a complex with a mono-coordinator or multi-coordination phosphine or lindenite ligand.口 3 · t1. Method, in which the homogeneous catalyst system is prepared in the reaction medium-Bin: Qujiao origin. The method according to item 1 of the patent application park, where the heterogeneous catalyst is separately outsourced, contains iron and / or copper. According to the method of covering the first item of the patent application, the heterogeneous anti-monitoring agent used is a responsible catalyst. According to the method of the scope of application for patents No. 1 or '&, the heterogeneous catalyst used is a kind of zeolite containing inscription-two-oxygen H, trans-L silicate Sheng' alumina zeolite and. Body load catalyst. The method according to item 1 or 5 of the scope of patent application, in which a heterogeneous catalyst containing exemption is used. -24- The national standard (CNS) of this paper is applicable to the standard (210 > < 297 public directors) (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 391955 Fasting Amendment 丨 4. Application for patent scope 1. 7 methods for preparing acetals by reacting alcohol with propyl ether, which are in the liquid phase. The existence of homogeneous catalysts for the organometallic compounds of Shu, Lu, Lu, Ship, 钺, and / or Iridium i contains one or more periodic table of elements. I, molybdenum, tungsten, chain, ruthenium II:. , Heterogeneous catalysts of rhodium, iridium, iridium, palladium, and / or elements are reacted in the presence of essentially anhydrous conditions. 2. ^ The method according to item "Scope of the Patent," in which the homogeneous catalyst used for the brand is platinum-a complex with a mono-coordinator or multi-coordination phosphine or lindenite ligand.口 3 · t1. Method, in which the homogeneous catalyst system is prepared in the reaction medium-Bin: Qujiao origin. The method according to item 1 of the patent application park, where the heterogeneous catalyst is separately outsourced, contains iron and / or copper. According to the method of covering the first item of the patent application, the heterogeneous anti-monitoring agent used is a responsible catalyst. According to the method of the scope of application for patents No. 1 or '&, the heterogeneous catalyst used is a kind of zeolite containing inscription-two-oxygen H, trans-L silicate Sheng' alumina zeolite and. Body load catalyst. The method according to item 1 or 5 of the scope of patent application, in which a heterogeneous catalyst containing exemption is used. -24- The national standard (CNS) of this paper is applicable to the standard (210 > < 297 public directors) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs