JPS5849338A - Preparation of alpha, beta-unsaturated carboxylate - Google Patents

Abstract

PURPOSE:To obtain titled substance in high yield with suppressing the formation of by-products caused by dehydration of a fatty alcohol, by bringing an alpha-oxycarboxylic acid amide as a raw material into contact with the first solid acid catalyst, followed by bringing the reaction mixture and the fatty alcohol into contact with the second catalyst. CONSTITUTION:An alpha-oxycarboxylic acid amide such as alpha-oxybutyric acid amide, etc. shown by the formula (R1 and R2 are H or alkyl with the proviso that at least one is alkyl) is brought inot contact with the first solid acid catalyst preferably in the presence of water. The prepared reaction mixture and a fatty alcohol such as methyl alcohol, etc. are brought into contact with the second solid acid catalyst, to give the desired compound. Yttrium phosphate, etc. are cited especially preferably as the first solid acid catalyst, and zirconium phosphate, etc. are cited especially preferably as the second catalyst. The reaction temperature is especially preferably 200-450 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing α, β-, β-carboxylic acid esters.

! ! Fortunately, the present invention uses a solid @ as a catalyst to
- Oxycarboxylic acid amide, water and aliphatic alcohol reaction field all related to a method for producing α,β-unsaturated carboxylic acid ester.

As a method for killing α,β-unsulfated carboxylic acid esters, such as methyl methacrylate, acetone cyanohydrin is used as a method for killing α, β-unsulfated carboxylic acid esters, such as methanol and methacrylamide sulfate. The method of esterification using This method has been carried out industrially, but -sulfur Cl
The drawback is that a large amount of N4* and low-value material of the device material is stiffened due to k.

The Ministry of the Invention et al. As a result of intensive research on a method for producing α,β-unsaturated carboxylic acid and its ester from cyanohydrin without further exposure, we have found that α-oxycarboxylic acid amide obtained by the irrigation reaction of cyanohydrin and water and/or water can be used in plants. At temperatures above 1150°C, aliphatic alcohols react in the gas phase.

Liquid phase Mayu is a gas-liquid mixed phase, with a catalyst in the solid #? A method for producing α,″β-unihydrated carboxylic acids and their esters by reacting them with

(Japanese Patent Application No. 143591/1982) for which the invention was filed.

By this method, a mixture of α-oxycarboxylic acid amide and water and/or alcohol is brought into contact with a catalyst,
There is no inconvenient decomposition or obstacles such as mounting tables, and the yield is high.
Alpha, beta-unsaturated carboxylic acids and esters thereof can be produced.

In addition, in conventional methods, the nitrogen content in the raw materials is extracted as low-value by-products such as wax wax.

In this method, it can be extracted as alkylaquines and/or ammonia, which are industrially heavy intermediates.

However, when preparing α,β-unsaturated carboxylic acid ester gold using this method, the desired α.

In addition to the β-unsaturated carboxylic acid ester, ether is produced as a by-product due to the dehydration reaction of the aliphatic alcohol. The amount of ether by-product t varies depending on the type of catalyst used and the reaction conditions. Catalysts and reaction conditions that produce a large yield of α,β-unsaturated carboxylic esters produce a large amount of ether by-product. .

As a by-product of ether, α, β-unsaturated carbon esters not only complicate the refinery process, but also α, β
- There is a problem in that the unsaturated force is uneconomical as a method for producing esters.

The present inventors have conducted extensive studies on the method for producing α, β-, and β-carboxylic acid esters using α-oxycarboxylic acid amide as a raw material, and methods for suppressing ether by-products as much as possible or suppressing them to light sound. The method of the present invention was mainly used for the production of fixed lees.

That is, in the method μ of the present invention, an α-oxycarboxylic acid amide obtained by a hydration reaction of cyanohydrin and an aliphatic alcohol are reacted in a gas-liquid phase to a gas-liquid mixed phase using a solid acid catalyst. The α-oxycarboxylic acid amide t, preferably the first
of the solid acid catalyst and then the resulting reaction mixture r with the fatty extended alcohol together with the second solid 6! With a catalyst! This is a method for producing α, β-, β-carboxylic acid esters by mixing the aliphatic alcohol with the ether by-product 1 due to the dehydration reaction of aliphatic alcohol.

Solid rRpf used in the method of the invention! A catalyst containing at least one phosphoric acid salt, sulfate, and oxide of a metallic element and a nonmetallic element of fia, , activated carbon, cation exchange ant, α-boron and nickel gold, etc.

More specifically, it is a solid phosphoric acid catalyst and a catalyst in which phosphoric acid is supported on a known carrier such as diatomaceous earth and subjected to appropriate thermal calcination.

In addition, a solid acid catalyst containing phosphate and Fi, 1α, 16, ■α, 116.111α, WIb,
Lanthanide, actinide, ■ α, yb.

Va, V6. V (b, an element selected from the b and group II elements, Li, Nα, Rh.

Cm, Be, Mg, Ca, Sr%Ba, SC, Y.

Mu, Fa, Co, Ni, Cu%Ag, Zn.

Cd, 8% A1. Ga, In% TI% Sn, pb
, a mixture of two or more phosphates of at least one element such as sb and B-5, or 1J of these phosphates? It is a touch sister that contains. The atomic ratio of these elements (denoted as Ai, !) and phosphorus (denoted as P) in the phosphate is set in the range of 0 to 3 (here, M
/P=o with internal phosphoric acid). The structure of these phosphates is not limited in any way, as long as the atomic ratio (M/P) between the above elements and phosphorus satisfies the range of 0 to 3.

These phosphates can be produced by any known method. Tomoe is generally a stile, 7 reparatives.
In-Okanitsuk Reactions Volume 2, No. 139
~1671.1965 [Preparative I
organic reactions 2゜139
-167 (1965)), namely, the method described in 金氎, 金＠Adaptation (Nakama fC, 怀金-you and phosphoric acid'!
Alternatively, it can be produced by a method of reaction-zetazing a phosphate. It was a cabinet. It may also be produced by a special method such as a method of producing by reacting gold phosphoric acid with phosphoric acid.

Catalyst Containing Phosphate 1: Mix the above-mentioned phosphoric acid I, other sulfuric acid as necessary, and W4 oxide with a commonly known carrier such as activated carbon, silica, silica-alumina, alumina, etc. It can be manufactured by mixing by a known method such as a method or a dipping method. For example, if gold member oxide is added in excess to phosphoric acid, the reaction σ
It is also possible to produce a mixture catalyst of gold ring oxide and phosphate.

Well, sulfur! A solid acid catalyst containing 1!2 salt, Li
, Na, K, Hb, Ca, Ha, Mg, Ca, Sl'',
Ha, CrlMn, P's, Co, Ni, Csb, Zn
.

The catalyst is a sulfate or a fusible macula salt of at least one element selected from Cd, 41% In, Sn, and □Pb, or a sulfate of these or a fusible sulfate salt.

In addition to the solid acid catalyst containing all of these sulfur #I salts, the above-mentioned gold sulfate salts are added with acidic sulfuric acid and, if necessary, other gold #I salts.
It can be produced using a 4m compound, a phosphate, a carrier, and any of the commonly known methods such as the crosstalk method and the dipping method.

Furthermore, He,
Mg, Y, La, Cg, Th% U, Ti, Zr.

V, Cr%Mo, W, un%Fa, Co, Ni.

Oxides of at least one element selected from Cm, Zn%Cd, H, Al, Si, sb, and Bi, conjugated oxides that are mixed oxides of 112 or more elements, or oxides thereof things and phosphates.

It is a mixture with a sulfate or a carrier. As a carrier,
Known activated carbon, silica, aluminum, silicon carbide, etc. can be mentioned. Catalysts containing these oxides or composite oxides and other catalyst constituents.

It can be produced by known methods such as λ, #i, precipitation method, immersion method 1, etc.

Among these solid acid catalysts, the first and second solid circles in the method of the present invention are selected, and they may be the same or different depending on the subject, however, the first solid acid catalyst As a catalyst, ri, especially Ia, ■α, ■α, [1
6. Lanthanide, actinide % Vat7t is a complex of ■group b phosphate, silicon oxide] α or [group 6 element oxide! r oxide or wb group element oxide and A1
6 or ■ Composite oxide with α-group element oxide Tomotoeharinsan aluinicum, magnesium phosphate, sodium phosphorus, yttrium phosphate, rinba)/tan, cerium phosphate, praseodymium phosphate, phosphoric acid Barium, bismuth phosphate, calcium phosphate, manganese phosphate, sodium magnesium phosphate, and oxidized materials include magnesium oxide and silicon oxide, and aftm materials of titanium oxide and magnesium oxide.

Alternatively, the catalyst may fail if it contains at least one kind of zirconium oxide and oxidation damage. %
Preferred examples of phosphorus include yttrium, phosphorus lanthanum, cerium phosphorus, graseodium phosphorus, aluminum phosphate, heptium magnesium phosphate, and catalysts containing W, a combination of magnesium oxide and silicon oxide. .

-Among others, as a solid acid catalyst of 10,000%@2.

瓜α, 176, 'dbma7t is the phosphate of iron group elements, y
Oxides of group b elements, silicon oxide and ■ alpha 7' (are ■ group b elements*# compounds, such as phosphorus, aluminum, iron phosphate, molybdenum, tungsten phosphate, Phosphorus [Umami titanium, zirco phosphate oxide, composite oxide of titanium oxide and silicon oxide.

A catalyst containing at least one kind of composite oxide of zirconium oxide and silicon oxide can be used. Particularly preferred are catalysts containing a% zirconium phosphorus, titanium phosphate, titanium oxide, and zirconium oxide.

The α-oxycarboxylic acid amide used in the method of the present invention has the general formula (1) (wherein 81 and R1 represent hydrogen and alkyl groups. ) is a compound represented by Examples of the higher α-oxycarboxylic acids include lactic acid amide, α-oxybutyric acid amide, α-oxyisobutyric acid afdo, α-oxyvaleric acid amide, α-oxyisoyoshio afdo, and α-oxyisoyoshio afdo. A variety of α-oxycarboxylic acid amides such as α-methyl-α-oxybutyric acid amide and α-methyl-α-oxybutyric acid amide can be obtained.

(9) The aliphatic alcohols used in the method of the present invention include /ethyl alcohol, ethyl alcohol, deglopylic alcohol, coglobil alcohol, monobutyl alcohol, ethylene glycol, ethylene glycol monomethyl ether.

Various aliphatic alcohols and substituted aliphatic alcohols such as glopylene glycol monomethyl ether are mentioned, and the alcohol is selected from these alcohols depending on the purpose.

In the method of the present invention, one reaction can be carried out by contacting a reactant with a solid acid catalyst, or by either a gas phase method or a liquid phase method; is preferable, and any method such as a fixed bed method or a fluidized bed method can be used.

In the process of the invention, the α-oxycarboxylic acid amide, preferably together with water, is brought into contact with a first solid acid catalyst, and then the resulting reaction mixture is brought into contact with a second solid acid catalyst together with the aliphatic alcohol, without separation. α,β- by contacting with acid catalyst
Unsaturated unsaturated fulvic/acid esters.

There is no particular restriction on the t of the raw material m* used, but it is usually α-
Water is 0 to 20% per mole of oxycarboxylic acid amide.
10 moles, preferably 1 to 50 moles of H, and the aliphatic alcohol reacted with the reaction mixture ranges from 1 to 200 moles, preferably 1 to 50 moles. The reaction temperature, reaction pressure, contact time, etc. may be the same or different between the contact reactions between the first and second solid acid catalysts, as long as they are within a linear range. That is, the reaction temperature If is 150°C ~
500°C, particularly preferably 200°C to 450°C.

Can the contact time with the substance be varied over a wide range depending on reaction conditions such as catalyst 1 reaction temperature?

The object of the present invention can usually be achieved within a range of 0.5 to 360 seconds. The reaction pressure may normally be atmospheric pressure, but may also be under increased pressure or reduced pressure. In carrying out the reaction, the reaction raw materials are accompanied by an inert gas such as nitrogen gas and brought into contact with the catalyst layer. Furthermore, although it is not necessary, the reaction may be started after ammonia or aqueous ammonia is supplied to the goose medium layer as a pretreatment of the @ medium.

The following is a testimonial from a friend who specifically explains the method of the present invention]
shows.

In addition, the display formula of the catalyst containing phosphorus #R used in the examples does not necessarily refer to the tonne contained in the catalyst or showing the structure of the #l salt, but to the above-mentioned metal and phosphorus in the phosphorus cg salt. This is a book that shows the atomic ratio (M/P). Friendly, the phosphate under the reaction conditions.

Even if it has a condensed phosphorous structure such as a metaphosphate or birophosphate, it is expressed as the corresponding orthophosphate as a tactile expression.

Example 1 Zirconium oxychloride (Zr0C118H,O)36
．． 1f (0,112 mol) total water s OmlKfgWl, tLttJ'v acid 1 S) IJ') Mu salt (N
a1i, PO4-2H,O)156,t (1 mol)
When dissolved in 1y2ooy of t3 normal salt and added under stirring to a solution heated to 80°C, a white precipitate is generated. After stirring for 1 hour, the white precipitate was thoroughly washed with water by decantation, and P was separated.

Wash with water and then. The resulting bright white precipitate was dried at 1'20°C and calcined in air at 400°C for 6 hours.
Molded into mesh granules and prepared Zr (HPO,) as a catalyst.

a conversion: / CL (L, O,) 21.2 t (
(LO65%) dissolved in nitric acid/I! Dissolve completely in 1
Is lanthanum nitrate a concession to L heating? A lanthanum nitrate water bath solution was prepared by adding water to the solution (400 CCcl). Next, sodium hydrogen phosphate (Na, HPO4)2α39(
A white precipitate is formed when 1 liter of occ is added to a water bath containing 143 moles of α. Stir this at 80°C for 1 hour.
Vs white precipitate? Wash thoroughly with water by decantation method,
It was separated by filtration and washed with water. 12 pieces of the obtained white plate
After drying at 0°C and firing at 400°C for 6 hours in an air stream, 1O-16 mesh granular VC was molded to form LaPO.
, the catalyst was prepared.

Pyrex reaction tube (9) with an inner diameter of 12 m shown in Figure 81
) Zr (HPO, ) in the latter stage catalyst 1i1 (6)! Catalyst 5CC'ft light + S, front stage catalyst layer (5) V'CLaP
O, contact@s CC was filled, and the evaporator section (43) was filled with a molten alumina bowl with a diameter of 3 mm. It was fixed in an electric furnace and connected to a reaction reactor (8) immersed in a dry ice strung as shown in Fig. 1. Next, the carrier cass feed fr (
3) From nitrogen gas 2 < ad 1 minute, it passes into the catalyst layer and the catalyst 1
i1 bun? Both the front stage and the t & stage were set at 275°C. Feed methanol fL from raw material feed #B (2) at a rate of 5 t/hr, then feed 47 tons from raw material feed pipe A (1).
α-oxyisobutyamide aqueous solution kLOf/h
The reaction solution during 3 to 4 hours after the start of raw material supply is collected at a rate of 100% and analyzed by gas chromatography.
- Molar yield of methyl methacrylate to oxyisoacetic acid amide f18Q, 0%.

Acetone is added to the reaction products other than methyl methacrylate.
4-(Molar yield based on α-oxyisobutyric acid ide) Dimethyl ether was not detected.

夾k ga 2-7 The catalyst and reaction temperature were changed as shown in Table-1, but the experiment was carried out using the same equipment and method as in HJ 1. The phosphate catalyst used was prepared by conventional known methods. That is, after directly reacting gold@nitrate, gold-chloride, or gold@oxide with 85 tidine #/l in a phosphate r water bath solution, evaporation to dryness or the formation of the aqueous solution. Sun #salt? Solid 1k obtained by separation and washing with water
It was thoroughly dried at 120°C. In this way, the KtA-produced phosphate and the commercially available phosphate were molded into pellets, and 2
After firing at 50° to 600°C for 5 hours, it is crushed into particles of 10 to 16 meshes and used as a catalyst. Of the oxide catalysts, Si01-MgO is treated in a sodium silicate water bath or a magnesium chloride water bath. The resulting precipitate was thoroughly washed with water, dried on a dry bed, and phosphoricated at 500°C for b hours.
The catalyst was crushed into 6 mesh particles. Mayu, Ti0
1#-1'l°ic! 4. After bathing in cold water, heat and hydrolyze, and wash the resulting precipitate thoroughly with water, then use Fit! Dry cleaning%
The mixture was calcined at 500° C. for 5 hours and crushed into particles of 10 to 16 pieces/unit to prepare a catalyst. Furthermore, Zr01 is Zr0C1
Aqueous ammonia was added to the aqueous solution, and the resulting precipitate was thoroughly washed with water, filtered and dried, incubated at SOO°C for 5 hours, and crushed into particles of 10 to 16 meshes to obtain a catalyst.

, Compare the catalysts used, reaction temperature hardening, and results in Table-1.
ul 1-8 What is the relationship between the amount of methyl methacrylate produced and the lifetime amount of dimethyl ether produced when α-oxyisoesteramide, water and methanol are fed to a single catalyst? For this purpose, the same equipment as in Example 1 was used, and the front stage catalyst layer was fully filled with fused aluminum J balls with a diameter of 3mm, and the rear stage catalyst + YJ VC was the same catalyst t5α used in Example.
4 from the raw material feed pipe A(1) shown in Figure 1.
α-oxyisoacetic acid amide water bath liquid in 7-layer IT tank L
ot/hr.

Methanol t-1,5f/At- is fed together with a fastener. In addition, the results of Example 1 and colleagues in Table 2 are t?
Ota.

[Brief explanation of the drawing]

FIG. 1 shows the reaction apparatus used in Examples and Comparative Examples. The meaning of each symbol in the figure is as follows. 1: Raw material feed pipe A 2: Raw material feed pipe B 3: Carrier gas feed pipe 4: Evaporation section 5: First stage catalyst - 6: Second stage catalyst layer F: Reaction @ Beloved device 8 Ni Dry Ice Strassage 9 = Pyrex reaction tube Patent issuer Mitsui Toatsu Chemical Co., Ltd. 5

Claims (1)

[Scope of Claims] An α-oxycarboxylic acid amide compound represented by the formula (wherein R1 and R8 represent hydrogen or an alkyl group, provided that at least 10,000 are represented by an alkyl group) Specifically, the reaction mixture is reacted with a first solid acid catalyst in the presence of water.
A method for producing an α,β-,β-carboxylic acid ester characterized by contacting with a second solid #1 catalyst.