JPH0122252B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing 1,1-diesters or aldehydes. More specifically, in the presence of one or more metals such as palladium, rhodium, platinum, ruthenium, nickel, and cobalt and/or their compounds and a saturated aliphatic or aromatic halide having 1 to 7 carbon atoms, carbon The present invention relates to a method for producing a 1,1-diester or aldehyde, which is characterized by reacting a saturated aliphatic or aromatic carboxylic acid anhydride having 5 to 36 carbon atoms with hydrogen. By reducing carboxylic acid anhydride with hydrogen, 1,1-
Methods for producing diesters or aldehydes are already known, and a method using cobalt carbonyl or a Group 8 noble metal as a catalyst has been disclosed (Tokuko Sho et al.
No. 48-19285, U.S. Patent No. 3579566 and Japanese Patent Application Publication No. 1986-
62045). The method using cobalt carbonyl requires the presence of carbon monoxide in the reaction atmosphere in order to suppress the decomposition of the cobalt carbonyl catalyst, and the use of volatile cobalt compounds such as cobalt carbonyl during product separation by distillation etc. There is a strong possibility that it will volatilize and get mixed into the product.
In this respect as well, it cannot be said that the process is satisfactory as an industrial process. Further, the method described in US Pat. No. 3,579,566 using a Group 8 noble metal requires the use of organic phosphine, arsine, or stibine as a catalyst in combination with the noble metal compound.
However, compounds such as organic phosphine, arsine, or stibine used in combination with precious metals are extremely special substances as organic industrial chemicals.
It is also expensive. In addition, since the method disclosed in JP-A-55-62045 uses a strong protic acid together with an insoluble metal catalyst, there is a strong possibility that condensation polymerization of aldehyde groups in the product will occur, and there is a problem in terms of corrosion resistance. However, this method cannot be said to be industrially satisfactory. In view of the above points, the present inventors conducted intensive research on a rational method for producing 1,1-diester or aldehyde by hydrogen reduction of carboxylic anhydride, and found that palladium, rhodium, platinum, ruthenium, nickel, and cobalt. The present invention has been completed by discovering a new catalyst system comprising one or more metals and/or their compounds and saturated aliphatic or aromatic halides having 1 to 7 carbon atoms. That is, the present invention provides a combination of one or more metals and/or compounds thereof, including palladium, rhodium, platinum, ruthenium, nickel, and cobalt, and the number of carbon atoms is 1.
1, characterized in that a saturated aliphatic or aromatic carboxylic acid anhydride having 5 to 36 carbon atoms is reacted with hydrogen in the presence of a saturated aliphatic or aromatic halide having 7 to 7 carbon atoms; This is a method for producing 1-diester or aldehyde. Although the detailed reaction mechanism of the hydrogen reduction reaction of carboxylic acid anhydride according to the present invention is not clear, the overall reaction can be expressed by the following chemical reaction formula. In the formula, R ₁ and R ₂ may be the same or different, but
The same case is preferable in practical terms because the number of types of products is reduced. The reaction represented by the above chemical formula is catalyzed by one or more metals such as palladium, rhodium, platinum, ruthenium, nickel, and cobalt and/or their compounds and a saturated aliphatic or aromatic halide having 1 to 7 carbon atoms. By using it as a compound, the reaction can proceed suitably. That is, according to the present invention, a specific metal carbonyl, phosphine, arsine,
It is not necessary to use an organic nitrogen group compound such as stibine or a strong protic acid as an essential component, and the combination of one or more metals such as palladium, rhodium, platinum, ruthenium, nickel, and cobalt and/or their compounds and the number of carbon atoms is 1 to 7. The use of saturated aliphatic or aromatic halides allows the reaction to proceed. That is, according to the method of the present invention, the desired product can be obtained in high yield under mild conditions, at a low catalyst concentration, and in a short reaction time, compared to conventional methods. Further, the metal catalyst is industrially advantageous in that it facilitates the separation and purification of the product or the separation and recovery of the catalyst, since the heterogeneous catalyst system described below can be selected as necessary. Metal catalysts can be utilized in any and all forms.
For example, the metal itself or in finely divided form, in the form of Raney metals or in the form of carbonates, oxides, peroxides, hydroxides, nitrates, sulfates, phosphates, halides, cyanides, thiocyanides, Sulfonates, _C1 - _C5 lower alkoxides such as methoxides or ethoxides, phenoxides, metal carboxylates in which the carboxy ion is derived from alkanoic acids of 1 to 20 carbon atoms, oxyhalides, hydrides, carbonyls, nitrites. , sulfites, phosphites, acetylacetone salts, sulfides, and compounds coordinated with ammonia, cyanide, amines, amino acids, etc. Some examples include Pd metal, PdX ₂ , PdX ₂ .
2H ₂ O, PdX ₂・2NH ₃ , Pd(CN) ₂ , Pd ₂ H, Pd
(OH) ₂ , Pd(OH) ₂・2NH ₃ , Pd(NO ₃ ) ₂ , Pd ₂ O,
PdO, PdO ₂ , PdSO ₄ 2H ₂ O, Pd ₂ S, PdS,
PdS ₂ , Pd ₃ (PO ₄ ) ₂ , Na ₂ PdX ₄ , K ₂ PdX ₄ ,
Li ₂ PdX ₄ , Pd(OAc) ₂ , Pd(AcAc) ₂ , PdX ₂
(PhCN) ₂ , Pd (SCN), Pd (NC) ₂ , palladium benzenesulfonate, Rh metal, RhX ₃ , RhX ₃・
3H ₂ O, Rh(OH) ₃ , Rh(NO ₃ ) ₃・2H ₂ O, RhO,
RhO ₂ , Rh ₂ O ₃ , Rh ₂ (SO ₄ ) ₃・6H ₂ O, RhS, [Rh
(AcO) ₂ 〕 ₂ , Rh ₂ (CO) ₃ , Rh ₆ (CO) ₁₆ , [RhX
(CO) ₂ ] ₂ , Rh (AcAc) ₃ , Rh (SCN) ₃ , Rh
(OPh) ₃ , Pt metal, H ₂ PtX ₆ , PtX ₂ , PtX ₄ , Pt
(OH) ₂ , Pt(OH) ₄ , PtO ₂ , PtO, Pt ₃ O ₄ , Pt
(CO)X ₂ , PtS, Pt ₂ S ₃ , Pt(CN) ₂ , Ru metal,
RuX ₂ , RuX ₃ , RuX ₄ , Ru(OH) ₃ , RuO ₂ ,
Ru ₂ O ₃ , Ru (NO ₃ ) ₃・6H ₂ O, Ru (CO) ₂ I ₂ , Ru
(CO) ₁₂ , Ni metal, NiX ₂ , NiX ₂・3H ₂ O, NiO,
Ni ₂ O ₃ , Ni(CO) ₄ , NiCO ₃ , NiSO ₄ , NiS, Ni
(CN) ₂ , Co metal, Co ₃ O ₄ , CoX ₃ , Co(OAc) ₂・
4H ₂ O, CoCO ₃ , Co ₂ (SO ₄ ) ₃ , CoSO ₄ , (X in the above formula is F, Cl, Br or I, Ph is phenyl group,
AcO represents an acetoxy group, and AcAc represents an acetylacetonate group. ) can be given. Furthermore, in the present invention, [Pd(PPh ₃ ) ₂ ]Cl ₂ , Pd
[(n- _C4H9 ) _3P ](CO) _Cl2 ,Rh( _PPh3 ) ₂ (CO ₎
Use metal complexes such as Cl ₂ , RhCl(PPh ₃ ) ₃ , Pt(PPh ₃ ) ₂ (SnCl ₃ ) ₂ , or organic nitrogen group compounds that can form coordination compounds with catalyst metals. No problem will occur if this is allowed. Also, Group 8 metals bonded to silica, polyvinyl chloride or polystyrene-divinylbenzene substrates cross-linked by phosphine, silyl, amine, pyridine or sulfide bonds [e.g.
CHEMTECH, 560-566p (1973); 117-122p
(1975) and others. ] It is also possible to use a metal polymer complex consisting of the following. As mentioned above, the catalytic metals are palladium, rhodium, platinum, ruthenium, cobalt, and nickel, and palladium, rhodium, platinum, and ruthenium are particularly effective. Of course, it is also possible to use a combination of these Group 8 metals. The metal catalyst can be used from the beginning or in a final state soluble in the reaction solution to form a homogeneous catalyst. Alternatively, insoluble or only partially soluble forms can be used, resulting in a heterogeneous catalyst system. In the case of a heterogeneous catalyst system, it is possible to use the Group 8 metal compound or the metal itself in the form of finely pulverized metal or Raney metal, but it is also possible to use it by supporting it on a carrier as described below. You can also. In this case, the supporting method may be, for example, a conventional dipping method, kneading method, adsorption method, coprecipitation method, ion exchange method, etc., but other methods are also possible. To give some examples, a carrier is impregnated with a solution containing the Group 8 metal or Group 8 metal compound and other components as necessary, and then formalin, hydrogen, sodium formate, carbon monoxide, and sodium are impregnated into a carrier. This is carried out by modifying the metal compound into a metal using ordinary reducing means such as boron hydride, lithium aluminum hydride, or hydrazine, and drying it, but it is not limited to these methods. Any method may be used as long as it can support the Group 8 metal and/or its compound. Supports used include carbon, graphite, bone char, alumina, silica, silica alumina, barium sulfate, zeolite, spinel, alumina with magnesia, thoria,
Titanium oxide, zirconium oxide, thorium oxide,
Lanthanum oxide, cerium oxide, zinc oxide, tantalum, clay, diatomaceous earth, celite, asbestos, pumice, bauxite, white clay, Super-Filtrol
Natural and treated clays such as silicon carbide, zeolite and zeolite molecular sieves, ceramics, boria, cement etc. are preferably used, but preferably carbon, graphite, bone char, alumina,
Silica, silica alumina, barium sulfate, zeolite, spinel, and alumina with magnesia are used. The carriers are used as particles of uniform and non-uniform size and capillary shape and optionally in forms such as moldings, extrudates, ceramic rods, balls, broken strips, tiles and the like. As described above, it has been disclosed that the metal catalyst according to the present invention can be used in the form of either a homogeneous catalyst or a heterogeneous catalyst, but it is preferable that the metal catalyst of the present invention can be used in the form of a homogeneous catalyst or a heterogeneous catalyst. Using a catalyst is a preferred embodiment. The reaction requires the presence of a halide along with a metal catalyst, but preferred halides have a carbon number of 1.
7 to 7 saturated aliphatic or aromatic halides or mixtures thereof. Typically, halides are CH ₃ I, CH ₃ Br, CH ₃ Cl, CH ₃ F, CH ₃ CH ₂ I,
CH ₃ CH ₂ CH ₂ I, (CH ₃ ) ₂ CHI, CH ₂ I ₂ , CHI ₃ ,
CH ₂ ICl, CHI ₂ Cl, CH ₂ IBr, CHI ₂ Br,
Saturated aliphatic halides such as CH ₂ ICH ₂ I, CH ₃ CH ₂ I

【formula】

【formula】

【formula】

It exists in the form of an aromatic halide such as [Formula] or any mixture thereof, and can be introduced into the reaction solution as it is. However, it is sufficient to introduce into the reaction solution a substance in which any one or more of these halides, ie, saturated aliphatic halides or aromatic halides, is produced in the reaction solution. Substances that react with other components in the reaction solution to form saturated aliphatic halides or aromatic halides include inorganic halides, such as alkali metal halides such as lithium, sodium, potassium, and magnesium. , alkaline earth metal halides such as calcium or metal halides such as aluminum, zinc, copper, lanthanum or cerium, and chlorine,
There is bromine or iodine. Among the halides mentioned above, it is a particularly preferred embodiment to use methyl halides such as methyl chloride, methyl bromide, and methyl iodide from the viewpoint of corrosion resistance of the reactor or separation and purification of reaction products. be. According to the invention, the reaction rate depends on the amount of Group 8 metal catalyst used, the halide concentration and the temperature. The amount of Group 8 metal catalyst used in the present invention varies depending on whether a homogeneous catalyst or a heterogeneous catalyst is used, and in the case of a heterogeneous catalyst, whether the reaction is performed in a fluidized bed or a fixed bed. In principle, any range of dosages can be applied. However, in general, 1×10 ^-4 to 25% by weight based on Group 8 metals, based on the reaction solution,
Preferably, a range of 5×10 ⁻⁴ to 20% by weight is selected, more preferably a range of 1×10 ⁻³ to 15% by weight, and a range of 2.5×10 ⁻³ to 10% by weight is particularly effective. Further, the amount of the halogen compound used together with the Group 8 metal catalyst is 10 ^-3 to 15 mol, preferably 10 -2 to 5 mol, more preferably 10 ^-2 to 5 mol per halogen atom based on the total volume of the reaction solution. It is used in a range of 10 ^-1 to 3 moles. The reaction temperature for carrying out the method of the present invention is suitably in the range of 20 to 500°C, preferably 30 to 350°C, more preferably 40 to 250°C. The total reaction pressure is also not a critical parameter in the production, as long as it is sufficient to keep the reaction liquid in the liquid phase and the hydrogen at a suitable partial pressure. The preferred partial pressure of hydrogen is 0.5 to 350 atm, optimally 1 to 300 atm, and even more optimally 2 to 350 atm.
The pressure is 200 atm, but a wider partial pressure range of 0.05 to 1000 atm is also acceptable. The hydrogen used does not necessarily have to be of high purity and may contain carbon monoxide, carbon dioxide, methane, nitrogen, rare gas, etc. The raw material gas may be supplied in the form of synthesis gas (mixed gas of carbon monoxide and hydrogen). In this case, although there is a strong possibility that carbon monoxide will be mixed in the hydrogen gas, carbon monoxide in the reaction gas tends to stabilize the catalyst and suppress side reactions, and this is a preferred embodiment in many cases. However, extremely low purity hydrogen is undesirable because it increases the pressure of the reaction system. Therefore, raw material gases with a hydrogen purity of 2 mol% or less should be avoided, preferably 5 mol% or more, and more preferably 5 mol% or more.
A raw material gas containing 10 mol% or more of hydrogen is preferred. Preferred raw materials used for the hydrogenation reaction of the present invention are acid anhydrides consisting of the same carboxylic acids such as propionic anhydride, butyric anhydride, isobutyric anhydride, caproic anhydride, valeric anhydride, stearic anhydride, benzoic anhydride, etc. mixed acid anhydrides consisting of any two types of carboxylic acids such as acetic acid and propionic acid, acetic acid and benzoic acid, intramolecular carboxylic acid anhydrides such as succinic anhydride, adipic anhydride, phthalic anhydride, etc. is a saturated aliphatic or aromatic carboxylic acid anhydride having 5 to 36 carbon atoms. The presence of water in reaction materials is a common phenomenon, but hydrogen and carboxylic acid anhydrides can tolerate the presence of a small amount of water, which is often present in commercially available reactants, and there is no problem. Does not occur.
However, the presence of more than 10 mol% of water in one or more of the reaction raw materials used in the present invention should generally be avoided, as introducing too much water into the reaction system may lead to decomposition of the raw materials and products. easy. In this respect, it is desirable that the water content be 5 mol% or less, more preferably 3 mol% or less. Since water is not a reaction product, maintaining near-anhydrous conditions in the reaction solution is easily accomplished by maintaining proper dryness of the necessary reactants introduced into the reaction zone as well as the reaction working fluid. Ru. In the method of the present invention, the carboxylic acid anhydride itself, which is a raw material, also serves as a solvent, so a solvent does not necessarily have to be used, but it can be used if necessary.
Commonly usable solvents include organic acids such as acetic acid, propionic acid, butyric acid, methyl acetate, ethyl acetate, ethylene glycol diacetate, propylene glycol diacetate, dimethyl adipate, methyl benzoate, ethyl benzoate, dimethyl phthalate, Organic acid esters such as diethyl phthalate, dioctyl phthalate, phenyl acetate, tolyl acetate, hydrocarbons such as dodecane, hexadecane, benzene, naphthalene, biphenyl, triphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate Examples include inorganic acid esters such as ate, tetramethyl orthosilicate, and tetrabutyl silicate, aromatic ethers such as diphenyl ether, and ketones such as acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone. The process of the invention can be carried out batchwise, semi-continuously or continuously. Further, in the case of a heterogeneous catalyst, the reaction type can be carried out in either a fluidized bed type or a fixed bed type. Hereinafter, this will be explained in more detail with reference to Examples. Example 1 40 g of propionic anhydride, 5.0 g of ethyl iodide, and 1.35 g of 5% Pd activated carbon (commercially available) manufactured by Engelhard Japan were placed in a pressure-resistant reactor, and hydrogen was pressurized to make the gauge pressure 100 Kg/cm ² . Heat to 175℃,
Stirring was continued at this temperature for 30 minutes. A significant pressure drop was observed during this time. When the contents were cooled and analyzed, 6.48 g of propionaldehyde and 2.65 g of propylidene dipropionate were produced along with propionic acid. Example 2 40 g of propionic anhydride, 5.0 g of methyl iodide, and 1.35 g of Pd activated carbon (commercially available) manufactured by Nippon Engelhard were placed in a pressure-resistant reactor, and while supplementing hydrogen, the gauge pressure was maintained at 30 Kg/cm ² and heated to 175°C. When reacted for 30 minutes with propionic acid, 6.16 g of propionaldehyde and 2.01 g of propylidene dipropionate
g was produced. Comparative Example 1 The same operation as in Example 1 was carried out without using ethyl iodide. No formation of propionaldehyde or propylidene dipropionate was observed. Examples 3 to 18 An acid anhydride, a Group 8 metal catalyst, and a halide were placed in a pressure reactor and reacted under predetermined conditions. The results obtained are summarized in Table 1. In Table 1,
The pressure represents the pressure at which hydrogen was introduced before the temperature was raised, and hydrogen was not replenished. Examples 3, 4, 5, 6,
Catalysts 7, 8, 9, 12, 17, 18, and 19 were commercially available from Nippon Engelhard. Examples 10, 11,
As catalyst No. 14, a commercially available product manufactured by Kawaken Fine Chemicals was used.

【table】

【table】

Claims (1)

[Claims] 1 Palladium, rhodium, platinum, ruthenium,
In the presence of one or more metals such as nickel and cobalt and/or their compounds and saturated aliphatic or aromatic halides having 1 to 7 carbon atoms, saturated aliphatic compounds having 5 to 36 carbon atoms Alternatively, a method for producing a 1,1-diester or aldehyde, which comprises reacting an aromatic carboxylic acid anhydride with hydrogen.