JPS60188342A - Synthesis of acetone - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a solvent for acetyl cellulose, etc. safely, selectively in high yield, by oxidizing propylene with oxygen by the use of a specific complex catalyst under mild conditions, simplifying preparation processes including purification process. CONSTITUTION:By the use of a complex catalyst comprising a complex shown by the formula I (M is transition metal belonging to group I , group IV-VII, or iron group of group VIII of periodic table; L is organic phosphorous compound; m and n are figure fixed by valence of transition metal and valence of anion; l is figure of coordination) capable of being subjected to coordination bond, with O2, forming an oxygen complex, and a complex shown by the formula II (M' is transition metal belonging to platinum group of group VIII of periodic table; L' is nitrile, organic fluorine compound, L; m', n', and l' are m, n, and l) capable of being subjected to coordination bond with propylene, forming a propylene complex, activated propylene is oxidized with bonded oxygen activated by complex formation at low temperature close to room temperature at normal pressure, to give acetone.

Description

Detailed Description of the Invention (Field of Application of the Invention) (3) The present invention relates to a method for synthesizing acetone, and particularly to a method for producing acetone by oxidizing propylene with an oxygen complex.

(Background of the invention) Acetone is a typical aliphatic compound, and is used in large quantities industrially as a solvent for acetylcell, nitrocellulose, acetylene, etc., and is also used in pharmaceutical applications as a solvent for fats, resins, camphor, etc. It also serves as a raw material for the synthesis of many intermediate products, such as methyl isobutyl ketone, methyl isobutyl carbinol, methyl methacrylate, bisphenol A, and even ketene.
It occupies an important position in the chemical industry.

Industrial methods for synthesizing acetone are broadly classified into three types: (1) isopropanol dehydrogenation method, (2) cumene method, and (3) propylene oxidation method.

Among these, the dehydrogenation method of isopropanol uses Zno or Cu as a dehydrogenation catalyst at 300 to 500°C, 3a
It is said that the isopropanol reaction rate is about 98% and the acetone (4) selectivity is 90% (K, Wcissermen).
, H., J. Arpe, translated by Mitsuaki Mukaiyama, Industrial Organic Chemistry,
p 2 [i 6 , Tokyo Kagaku Dojin (1978)). In addition, the cumene method produces cumene in a liquid phase at normal pressure and 120°C.
Cumene hydroperoxide is synthesized by oxygen oxidation using U, Co, etc. as a catalyst, and this is heated to 0.1 to 2
% lI2SO4 and co-produces phenol and acetone. The selectivity based on cumene is about 90%, with phenol accounting for 60% and acetone accounting for 40%.

These processes are currently being carried out step by step,
A one-step method for producing acetone under milder reaction conditions is attracting attention using propylene as a raw material and palladium chloride (Pd (2) (1!2) - cupric chloride (Cu (2)).
C7! This is the so-called Wanoka method, in which z) is used as a catalyst, and is the most distinctive of the methods for producing acetones (see page 265 of the above-mentioned document).

In this method, the catalysts Pd(2)Cfz and Cu
(2) A composite catalyst in which CnH2 is dissolved in a salt@solution (p HO-2) is used. First, propylene is oxidized by divalent palladium (Pd (2)) and water to produce acetone (CH3COCH3). The reaction is shown by the following formula, and water is involved in the reaction.

CH3CH−CH2+ P d (2) C7+2 +
As can be seen from the H20 reaction equation, pa (2> is reduced to metal palladium (Pd(0)) and precipitated.

In addition to preventing this, CIJ (2) C7!
It is necessary to coexist pd (0) in multiple numbers and oxidize pd (0) to pd (2) and regenerate it as shown in the following formula.

Pd (0)→-2Cu (2)C112--Pd (
2) CI22+2Cu (1) CI! , ' (2) Furthermore, the poorly soluble Cu (1) CI2 produced as a by-product at this time is oxidized with oxygen according to the following formula in the coexistence of HCj2, and becomes Cu(
2) Sarel returns to C7!2.

2Cu (1) CI+ -0□+2HCI2→2CuC
j! 2 +H20(3) (6) Thus, pd (2)/Pd (0) and Cu
A redox system of (2)/Cu (1) is employed to enable continuous oxidation of propylene. However, as shown above, the oxygen molecule does not directly react with propylene, but instead, 1)(1(2)/l) d(0),C
u (2>/Cu (1)) Since the complex redox reaction of the thread is utilized, these are the rate-determining steps. In addition, during the reaction, sparingly soluble Pd (0) and Cu ( 1
) Cj! Since it generates a high concentration of tl C1, water/
8 liquid (p HO to 2) is employed, which necessitates the selection of corrosion-resistant materials.

Furthermore, since the solubility of oxygen in water is low, it is necessary to increase its solubility, and the higher the olefin, the lower the reactivity, so the reaction conditions are 14
The conditions are severe, such as 0°C and l 4 a trn. Note that under these conditions, the reaction rate of propylene was more than 99%, the selectivity to acetone was 92%, and 2
It is said that ~4% of propionaldehyde is produced as a by-product (see page 265 of the above-mentioned document). Additionally, if excess dissolved oxygen is released into the gas phase (7), propylene and oxygen will mix, potentially causing an explosion or other I/Rubble, and countermeasures will be required (Kihara et al., ed., revised). Complete manufacturing process diagram, von ■, p286, Kagaku Kogyosha (197B)).

In this way, both methods are carried out at relatively high temperatures and pressures, and are generally carried out under milder conditions.
There was a desire for a method that would allow the synthesis of

(Object of the invention) In order to solve these problems, the object of the present invention is to selectively oxidize propylene with the combined oxygen in the oxygen 1i, +7 form in one step under milder conditions to selectively oxidize acetone. The aim is to synthesize with high yield.

In short, the present invention uses a transition metal complex in which an oxygen molecule coordinates to a metal ion to form an oxygen complex as one of the catalyst components, and further coordinates propylene to a metal ion to form a propylene complex. This method uses a composite catalyst containing a metal complex to oxidize propylene activated by complex formation with bound oxygen activated by complex formation, and synthesizes acetone under mild conditions in a non-aqueous solvent system ( 8) Yes.

That is, the present invention has the following points: 1. In the method of synthesizing acetone by oxidizing propylene with oxygen in the presence of a total bending complex catalyst, an oxygen complex is formed by coordinating with oxygen as the total bending complex catalyst i) I complex (MmXn-Lito,
Using a composite catalyst containing a complex catalyst (M'm'Xn"・L'i') that can coordinate with propylene to form a propylene complex (where M is Group 1 of the periodic law, X is an anion such as a halogen, L is an organic phosphorus compound, M' is a transition metal belonging to the platinum group of Group II of the periodic table, L' is a class, organic fluorine compound or organic phosphorus compound, m, m', n, n'
is a number determined by the valence of the transition metal and the valence of the anion, and 1 and ρ1 mean the coordination number). The above m, m", n, n" are the number of elements of the transition metal ion,
and the number of anion elements, and β and β° represent the number of ligands, preferably 1 to 4.

Acids that are effective for oxidation reactions of various organic compounds (9) Various oxygen complexes that can be used as oxidizing agents have been investigated in vivo, such as copper hemoproteins and iron hemoproteins (Otsuka, Yamanaka, Metalloproteins, etc.) Chemistry, Kodansha, (1983)). However, there are extremely few examples of oxidation reactions of organic substances using oxygen enantiomers that have been carried out on an industrial scale.

The present inventors have conducted various studies on stable oxygen complexes made of transition metal compounds that can be used to oxidize organic substrates.

Typical examples include hexamethylphosphoramide (also known as tris(dimethylamino)) and hexamethylphosphoramide (also known as tris(dimethylamino)).
A solution of a complex (Cu(1)(1!・hmp a) with bosphine oxide (hereinafter referred to as hmp a)
6-118720 and 57-19013) are
It takes on a dark green color when in contact with oxygen.

When such a complex has the general formula MmXn-T-42, m=l, n-1, β-1. Also, Ti
(3) or V(3) is the central metal, and the anion is, for example, C7! -, the resulting complex is (10) T i (3) Cj! 3 ・hmp a,,V (3)
C/3 ・hmpa, m-1 and n・-3 respectively
, ρ...1.

By the way, normally, when a solution LSI of a Cu(]) compound absorbs oxygen, 111 m of low-atom copper is oxidized to divalent copper as shown in the following formula. CIJ (1) Cff -hmp a〆content/pi, L
A similar oxidation reaction occurred here, resulting in a green color.)

--CLl (2) +Or-T (4) However, 2(
lli copper compounds (C11(2) (1!2) and hm
The color of the solution of the complex with pa was dark red, indicating that no oxidation reaction was occurring. To further clarify this point, we measured the ultraviolet absorption spectra of each solution, and as shown in Figure 1, CIJ
(1) Spectrum of CI2-hmpa complex solution (/8 medium: ethanol) (1 in Figure 1) and spectrum of /8 solution in which the complex solution absorbs oxygen (2 in Figure 1) &;
J, divalent copper ij) body (CIJ (2) Cil!2 ・
(hrnpa)z)i'8/& spectrum (3 in Figure 1) was found to be completely different. From these results, C1" (1) C7!・In h m p a /8 liquid, even if oxygen is absorbed, the oxygen is absorbed by Cu(1) in the liquid.
It was hypothesized that CIJ(2) was not consumed to oxidize CIJ(2), but existed as a so-called oxygen complex, which was coordinated to CIJ(1) as an oxygen molecule.

Constant concentration of Cu (1)C7! -hmp As a result of measuring the amount of oxygen absorption in aQff solution, Cu (1)
The molar ratio of oxygen absorption to Ut is 2:1, and the following equation shows that Ut
It was found that this is the oxygen 61f form that is produced. Such an oxygen complex has not yet been reported.

2 Cu (], ) C7! -h m I) a→-
02--kai(Cu(1)C7!・hmpa))4 ・0
2 (5) This oxygen complex is stable, and oxygen oxidation of Cu(1) to Cu(2) by bound oxygen requires 10
So much so that it requires boiling at 0°C. Further, a feature of this oxygen complex is that the coordinated oxygen does not desorb even by heating or degassing under reduced pressure, that is, the oxygen absorption reaction is irreversible. For this reason, Cu
(1) After the Cf/hmpa complex solution is brought into contact with oxygen and J air to form an oxygen complex, excess M-separated oxygen can be easily removed by heating or vacuum degassing.

Therefore, in the oxidation reaction of an organic substrate by the bound oxygen of the present oxygen complex, it is possible to avoid unreacted oxygen remaining in the gas phase of the reactor, which is advantageous in terms of safety. Further, the 511 body of the present invention selectively absorbs oxygen from the air and forms an oxygen complex exactly like that of pure oxygen, so air is sufficient as an oxygen source.

On the other hand, acetone is synthesized by oxidizing propylene with bound oxygen activated by distributing it to a transition metal compound in a series of steps.
If it can be activated as a pyrene complex, the oxidation reaction can be performed at a lower concentration and pressure.

Therefore, we next conducted various studies on complexes of transition metals belonging to the platinum group of group Ⅰ of the periodic law. (13) If we talk about palladium chloride Pd (2)C7!2 as the front side, Pd (2)C12 is ``double h
A complex in which one or two molecules of hmpa are coordinated in mpa as shown in the following formula is formed and is well dissolved.

P d (2) Cj! 2 +2 h m pa
.

Pd (2) Ce2 ・ (hmpa) 2 (6) When this complex is mixed with the general M″m′ X n″・I4°l, ml−1, nl−2,7! '=2. In addition, when the central metal ion is Pt (2) or Ir (3) and the anion is 5042'', the resulting complexes are Pt (2) SO4 (hmpa) 2 and Ir (3), respectively.
2 (SO4)3 ・ (hmpa)z, the former is ml-1, nl-1, 11-2, and the latter is ml-2,
nl-3,7! '-2.

First, a gas absorption method was used to examine whether this Pd (2) CR2 (hmpa) 2 complex could coordinately bond propylene to form a new propylene complex. Zunawara, h m pa single solution system and Pd (2) (1
! When the absorption amount of propylene was measured comparatively for the 2.(hmpa)2 complex solution system, (14) there was no change in both, and the absorption amount was 4J as a solvent.
This is the value of physical dissolution for a. Therefore, the more stable propylene 1.・N11 forms a body and Frupa (2) Various tests were conducted regarding the complex.

As a result, to give a representative example, as a modified ligand (auxiliary complexing agent)
ff2- (hmp a) 2 i:j body? G? It was found that the propylene absorption amount increased in the system added to &. That is, the gas absorption amount of each solution of the hmpa/benzonitrile (PhCN) system and the hmpa/benzonitrile/Pd (2) (1!2 system) was measured, and the propylene absorption amount of each solution was compared as shown in Figure 2. Since it is a non-aqueous system, propylene absorption is large even in the solvent and modified ligand system (A> alone), but in the presence of pd (2) complex (B), the absorption amount increases. , it is clear that a stable complex of Pd (2) ions and propylene is formed.

That is, as a representative of nitriles, acetonyl-lyl (C
When H3CN) is added, a new complex is formed as shown below.

Pd (2) C112・ (hmpa) 2+CH3C
N-=Pd (2) CnH2.CH3CN-hmpa10hmpa (7) When propylene is bubbled through step t), a very stable propylene complex shown by the following formula is produced.

P d (2) C7!2 ・CH3CN-11rnp
a0CH3CH= CH2 -→Pd (2) Cff2 ・'C3H6-CH3CN
Nbmpa (8) Propylene is significantly activated in such stable complexes.

As described in 2 below, activated propylene is coordinated to Pd(2) ion as a propylene complex and activated by the bound oxygen in the oxygen complex described above in a non-aqueous solvent system under mild conditions. , can be oxidized in one step to synthesize acetone.

In other words, is it also a ligand? Cu (1) CIlCll using h mpa or other suitable solvent.
-h&M body and Pd (2) CnH2・CH3CN
・As described below, oxygen or an oxygen-containing gas such as air is passed through the solution containing the h m p a complex to obtain an oxygen complex at an appropriate concentration, and excess oxygen is removed by heating or degassing as necessary. and bubbled with 1/2 liter of propylene.
Forms a propylene complex. This complex formation activates pr', 1 pyl/n, C11', oxygen 11, which is oxidized by bound oxygen in the body at a low temperature, such as around 40° C., to produce acetone almost quantitatively.

This oxidation reaction is shown by the following equation.

(Cu (1) C1l ・hmp a) 202 t2P
d (2) Cl2-2・CH2=CHCl-1+ −
CI(:l CN+2 hmp a-ci2CH3COC
r+3+2Cu(])C1-t+mpa+2Pd (2
)C7! z ・CH3CN-hmpa (9) In this way, in the present invention, Pd(2) &! Coordinating with the body,
Since the activated propylene is oxidized to produce acetone, the valence of the central metal of the complex remains unchanged. Therefore, the mechanism of this synthesis method is completely different from conventional methods (methods that utilize an oxidation reaction between Pd (2) ions and water), and after the completion of the reaction, the product is purified by operations such as distillation. After separating the catalyst liquid and the catalyst liquid, air is again aerated into the catalyst liquid (17), and propylene is further aerated. According to reaction formulas (5) and (8), the oxygen complex and propylene complex are regenerated, and according to reaction formula (9), the oxygen complex and the propylene complex are regenerated. It has the great advantage of being able to repeatedly generate acetone.The same effect can also be obtained by aerating a mixed gas of propylene and oxygen in a range outside the explosive limit.Also, the reaction substrate oxygen and propylene are activated as a complex, it is possible to achieve a reaction rate superior to conventional methods at a temperature of about 40°C under normal pressure.Furthermore, since the reaction is conducted under mild conditions, it is possible to achieve a reaction rate superior to conventional methods at a temperature of about 40°C. As described above, there are fewer by-products and the selectivity can be improved.

The complex catalyst capable of forming an oxygen complex in the composite catalyst system of the present invention (Mm
V of group Ⅰ, Nb1 Cr of group Ⅰ.

MoXW, Group II Mn, Group II Fe, Co.

Salts such as Ni, etc. are preferable, and salts such as Cu(1), Ti(
3) , V (3) halides are preferred.

As the ligand I, trif(1) which is a derivative of phosphoric acid is used.
8) Phenylphosphine oxide, hexamethylphosphoramide, mono-, di-, and triesters formed from the reaction of phosphoric acid with methanol, ethanol, etc., and derivatives of phosphorous acid such as dimethyl methylphosphonate and methyl dimethylphosphinate. Preferred are organic phosphorus compounds typified by mono-, di-, and triester, phenylphosphonite, dimethylphosphinate, triethylphosphine, l-riphenylphosphine, etc. produced by the reaction of phosphoric acid with methanol, ethanol, etc. , especially hexamethylphosphoramide (hmpa).

On the other hand, a complex catalyst (M'
M' in m'Xn''L'Ro)
As m'
(2), pt(2) or Ir(3) halides are preferred. As the ligand L', nitriles such as acetonitrile propionitrile, benzonitrile, l-runi I-IJ, the above-mentioned organic phosphorus compounds, organic fluorine compounds such as fluorinated toluene, hesitrifluoride, etc. are preferred, and nitriles are particularly preferred.

When the reaction is carried out in the /8/& state, the solvent used is acetone (b.

p. 56°C/760 dragon) fg) that can be easily separated is preferred. Such solvents include various solvents such as n-hexane, l-luene, cyclohexane, methyl isobutyl ketone, cyclohexane, ethanol, ethylene glycol, butyl acetate, propylene carbon-1-, chloroporum, chlorohenzene, pyridine, and tetrahydrofuran. Examples include at least one selected solvent or a mixture thereof. Also, the ligand I, or ■
, " is a liquid, it can also be used as a solvent.

In addition, composite complexes such as activated carbon, silicate, porous glass,
Alternatively, acetone can be synthesized by supporting it on a porous carrier such as a polymer having a giant network structure and oxidizing propylene with the bound oxygen in the oxygen complex.

If the reaction temperature is too low, the oxidation rate will be slow;
℃Ju or higher is preferable, and 60 to 80℃ is particularly preferable.

A higher reaction pressure is preferable because the oxygen absorption rate increases, the amount of propylene in the liquid increases, and the concentration of activated 1) 1, converted propylene increases, but even at normal pressure, the reaction rate is sufficient. It will be done.

In the present invention, by adding a basic solvent such as sulporan, dimethylsulporan, dinotyl sulbogide, dimethylformamide, trimethylmethane, dimethylsulpone, etc. to the complex/8 solution, or by using the II complex itself as a solvent. , can significantly accelerate the acetone production reaction.

Although the reaction of the present invention is carried out in a non-aqueous system, there is no problem with the presence of water in a range where no precipitate is produced.

Above, we have described 111 new complexes and their characteristics, as well as examples of synthetic reactions using them. Next, the present invention will be explained by examples.
, will be explained in more detail. Note that the gas volumes in the examples are values under standard conditions.

(21) (Embodiments of the invention) Example 1 Cuprous chloride (C11
(]) C7ri 5g (50 mmol) and hmpa
Prepare 325g, Cu (1) C7!・hmpai
A 330-meter-long tube was produced at Tobu. moreover(
Turtle's 500m1! Add palladium chloride (P) to a test tube with a stopper.
d(2)C7!2) 1.3g (7 mmol) and 130g of acetonyl-lyl were charged, and Pd(2)C7
! 2.(CH3CN)2&if body solution 170mn
was prepared. After that, both were transferred to a reactor with a capacity of 1 p.
C11(1) As Cβ, Q, l m o (2 /
1, Pd (2) 0.015mo7 as C7!2! /
7! complex catalyst solution (Cu(1)Cj!-hmpa/
Pd (2) C7+2・CH3 CN- hmpa/h
mpa-CH3 CN system) 500ml! was prepared.

When 2.5 liters of air was bubbled through this at 25°C and normal pressure, an apparent amount of 340 mn (14 mmol) of oxygen was absorbed, but when nitrogen gas was then bubbled through, the gas phase in the reactor The oxygen and the oxygen physically dissolved in the liquid (22) were removed. However, there are 260m+2 oxygen in the liquid and 111 oxygen bodies (0,011m
o n / 7 exists, and desorption of oxygen from the bound oxygen in this oxygen complex is not observed even by thermal deaeration, etc., and oxygen absorption due to the formation of oxygen tIY form is irreversible. It was recognized that

After these operations, propylene was heated at 25°C under normal pressure.
When the solution was aerated with p, 700 mβ was absorbed into the solution, and the propylene concentration in the solution became (1.06 m o 1 /l). was analyzed using Gasc l-171 graphy.

As a result, 0.51 g (8.8 mmol) of aretone was produced. The reaction between the propylene complex and the oxygen complex follows Equation (9) above, and in this example, since the propylene complex is present in excess with respect to the oxygen complex, the amount of acetin produced is , is regulated by the oxygen complex concentration. Therefore,
In this example, the acetone yield, expressed as the bonded oxygen group 111j in the oxygen complex, was 80%.

Example 2 The same operation as in Example 1 was performed except that the reaction temperature was changed to 40°C and 90°C, and the reaction was carried out for 30 minutes. As a result, 0.31 g (5.3 mmol) and 4.3 g (7.4 mmol) of acetone were produced, respectively, and the acetone yield was 48% at 40°C and 67% at 90°C. Met. In particular, when the reaction temperature is 90°C, propylene is noticeably desorbed into the gas phase of the reactor. It was found that the acetone yield decreased due to the decrease in the concentration.

Note that by increasing the pressure, it was possible to keep the propylene concentration in the liquid constant even if the temperature was increased.

Example 3 In Example 1, 0.57 g (9.9 mmol) of acetone was produced as a result of the same operation and reaction in which ace-1-nitrile was replaced with hendinitrile. By changing to nitrile, the acetone yield is 80% of that of acetonitrile.
It rose from - to 90%.

Example 4 In Example 3, the reaction temperature was set to 40° C., and the other operations and reactions were the same, and the acetone yield reached 85%.

Example 5 When the same operation as in Example 1 was performed except that the air was replaced with pure oxygen, no significant difference was observed in the oxygen complex concentration and propylene complex concentration in the liquid. When the reaction was carried out under these conditions, the acetone yield was 82%. Thus, in the present invention, the oxygen source does not need to be pure oxygen, and inexpensive air is sufficient.

Example 6 In Examples 1 and 3, hmp a was added to 50 g (0,
When the reaction was carried out using the same composition and conditions except for adding 8 g (0.1 mol) of henzonitrile and 240 g (2.0 mol) of sulporan, acetone was 0.
．． 63 g (10.8 mmol) raw (25) was produced. This is the yield based on bound oxygen in the oxygen complex” (:
It is 98%. Furthermore, by-products were also below the detection limit. It is shown that basic solvents such as sulfolane are very effective in improving yield.

Example 7 In Example 6, Pd (2) (Pt instead of J2)
(2) When the same operation and reaction was performed except that 8 g (0.03 mol) of Cβ2 was used, the acetone yield was 99%.
Met.

Example 8 In Example 6, Cu(L)C# was converted into cuprous bromide (Cu
When the reaction was carried out under the same conditions except for (1) Br), the acetone yield was 96%.

In addition, Cu (1) (1!
M), the ace1-one yield was 97%.

Example 9 In Example 7, PL(2)Cβ2 was replaced by pt(2)B
Let r2 and further set Cu (1) (1! to Cu (1) B
When the reaction was carried out as r, the yield of acetone (26) was 97%.

Example 10 The same procedure as in Example 6 was carried out except that hensitrifluoride was used instead of benzonitrile, and the acetone yield was 93%.

Example 11 In real can f row 3, h m p a is 85B.
When the reaction was carried out in the same manner except that 275 g of toluene was added as a solvent, the acetone yield was 92%, which was almost the same as in Example 3.

Example 12 In Example 6, air and P1:I pyrene were simultaneously reacted in the catalyst solution outside the explosion limit? &Amount/Gas ventilation rate -30
When I tried j + D at the ratio of h-1, I got 7 of 1 pyrene.
6% was oxidized to ace1-ene.

Example 13 In Example 6, u (1) C1,, P(](
2) Cβ2, hmpa, zonitrile, and sulborane were simultaneously added to the reactor. As a result, a homogeneous /8 liquid was obtained, and when the same reaction as in Example 12 was carried out, no significant difference was observed in the conversion rate of propylene to acetone. Therefore, it is clear that stepwise operations as shown in Example 1 are not necessarily required in this synthetic reaction.

Example 14 In Example 6, Cu(1)cz was replaced by V(3)Cn3
, V (3) (0.1mo as 1!3
12/i', P d (2') 0.015 m as C12.

500rr+j of e/1 catalyst solution! The same operation was performed except for the preparation. As a result, 0.014 m o (1
/ I! oxygen complex (160m+2 as bound oxygen) and o.

A propylene complex of 57 m o (1/j!) was formed. Then, when these were reacted at 40 °C for 30 minutes, 0.32 g (5.5 mmol) of acetone was obtained,
The acetone yield based on bound oxygen was 39%.

Example 15 In Example 14, (3) C7!3 was replaced with TiCl3, and T i (3) Cj! 30.1 mo
7! The same operation was performed except that the value was set to /l. As a result, an oxygen complex of 0,036 m o A'/R and 0.036 m o A'/R were obtained.
A propylene complex of 057 moA/p was produced. When these were reacted under the same conditions as in Example 14, the acetone yield was 42%.

Example 14 Giant reticular styrene-divinylhenzene copolymer beads (particle size approximately IHφ, specific surface area 700 to 800 nf/g
, Organo Amberly i X AD 4) 50m
j! was impregnated with a catalyst solution containing an oxygen complex having the composition shown in Example 6, followed by suction filtration to prepare a granular catalyst. This was filled into a hard glass reaction tube with an inner diameter of 20 mm and heated to 60°C.
After heating the propylene to 17! The product in the outlet gas was analyzed by gas chromatography. As a result, the product was only acetone, and the yield of acetone based on propylene was 4% for 2 hours from the start of the reaction.

Thereafter, the exit gas was recycled and the acetone yield on the basis of oxygen complexes reached 70%.

Furthermore, once the propylene supply was set to 1, air was aerated to regenerate the 0° bonds consumed in the reaction, and the oxidation experiment was repeated under the conditions (29) described in -, but the same results were obtained. Ta.

From the above, it has become clear that even when the complex of the present invention is supported on a porous carrier, the reaction due to the bound oxygen in the oxygen complex proceeds. Note that as the carrier, porous carriers such as silicates, activated carbon, porous glass, etc. can be used.
In addition to suction filtration, various methods such as heating gas aeration, low-temperature calcination, etc. can be used as a treatment method after impregnation.

Comparative Example 1 A catalyst solution was prepared in the same manner as in Example 3.11, except that no nitriles or organic fluorine compounds were added, and the same operations were performed. As a result, the yield of acetone was 0.1% or less in all cases. From these results, it is clear that the di-lyl-hydryl-organic fluorine compound as a modifying ligand changes the physical properties of the coordinated metal ion, forms a stable propylene complex, and greatly contributes to the activation of propylene. Shown.

Comparative Example 2 In a reactor similar to Example 1, Pd(2)Cβ2(30
) 1.3g and 325g of hmp a, Pd(2
)CR2・ (hmpa) 2&i+f form hmp a
An i solution was prepared. Oxygen is not vented to this, but its (l
! Propylene was aerated in the same manner as in Example 1 and reacted under the same conditions (60° C., 30 minutes), but propylene was not oxidized at all. In addition, metal palladium (Pd
(0)), indicating that oxidation by pd (2) ions did not occur in a non-aqueous solvent system such as h m pa.

Comparative Example 3 5 g of Cu (1) Cl was added to the complex solution prepared in Comparative Example 2, and Cu (1) C7! / P d (2)
A catalyst solution consisting of C122/h m pa was prepared and subjected to the same operations and reactions as in Comparative Example 2, but no oxidation of propylene was observed. aerate oxygen,
It was shown that it is necessary to form an oxygen complex.

Comparative Example 4 Benzier I.Ril was added to the mirror solution prepared in Comparative Example 3, and the same operations and reactions as in Comparative Example 2 were carried out, but in this case as well, no oxidation of propylene was observed because oxygen was not aerated. I couldn't.

Comparative Example 5 In Comparative Example 2, oxygen was bubbled through, but propylene did not react at all. This indicates that oxidation reactions due to free oxygen do not occur in the heathered yarn.

From the above Comparative Example 2.3, it is clear that the present invention has pd(2)C7!
It is clear that this method is completely different from the acetone synthesis method from propylene using the -Cu (2) C11 redox system as a catalyst.

Furthermore, when oxygen was bubbled through the catalyst solution containing the propylene complex in Comparative Example 4, acetone was produced in a high yield as in each of the aforementioned Examples.

From the above, the present invention differs from conventional methods in that it is a new method in which bound propylene activated by the formation of a propylene complex is oxidized by bound oxygen activated by the formation of an oxygen complex to synthesize acetone. It is shown that

(Effects of the Invention) According to the present invention, propylene and oxygen do not come into direct contact as free molecules, but by a specific composite catalyst system.
The desired acetone is selectively synthesized in high yield at a low temperature near room temperature and normal pressure by the reaction between propylene and oxygen, each of which is coordinately bonded to a transition metal ion and in an activated state. be able to. Furthermore, since the synthesis method of the present invention produces fewer by-products, the manufacturing process including subsequent purification is simplified. Note that even if air is used as an oxygen source, since oxygen is selectively absorbed, the same effect as using pure oxygen gas can be obtained. Furthermore, since oxygen absorption is irreversible, after forming an oxygen complex, there is no excess free! 1iIi
Oxygen can be easily removed, which is extremely advantageous in terms of safety.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the ultraviolet absorption spectrum of the complex used in the present invention, and FIG. 2 is a diagram showing the results of examining the formation of a propylene complex by a gas absorption method. Agent: Patent attorney Takenaga Kawakita (33)

Claims (1)

[Claims] (1) In a method for synthesizing acetin by oxygen-oxidizing propylene in the presence of a metal complex catalyst, an oxygen complex is formed by coordinate bonding with oxygen as the metal complex catalyst. A complex containing a complex (Mm'Xn'·L'β°) which can form a propylene complex as one of the catalyst components, and an &11-body catalyst (M'm'Xn'·L'β°) which can coordinately bond with propylene to form a propylene complex. Using a catalyst (where M is Group 1 of the periodic law,
A transition metal belonging to groups ■ to ■ or iron group of group 1, X is an anion such as a halogen, ■ is an organic phosphorus compound, M is a transition metal belonging to the platinum group of group II of the periodic rule, Lo is Nitriles, organic fluorine compounds or organic phosphorous compounds, m, m
', n, n' are numbers determined by the valence of the transition metal and the anion, and ρ and 11 represent the coordination number. (2. In the claims, m, m', n, (1) n1β, ff' are each 1 to 4. (3) In the claims 1 or 2 , the X is a halogen such as CA-1Br-1-, or CH
3Coo, BF4-1PF/, -1S042-, etc., an anion. A method for synthesizing acetone. (4) In any one of claims 1 to 3, the organic phosphorus compound as the ligands I1 and Lo is a compound represented by an alkoxy, alkyl or amide derivative of phosphoric acid or phosphorous acid. A method for synthesizing acetone characterized by the following. (5) In any one of claims 1 to 4, the solvent for the complex capable of forming an oxygen complex and the complex capable of forming a propylene complex is an aliphatic, alicyclic, or aromatic hydrocarbon. , at least one compound selected from the group consisting of oxygen-containing organic compounds, organic halogen compounds, and nitrogen-containing compounds, or when the ligand L' is a liquid, the ligand itself is used as a solvent. (2) A method for synthesizing aceline, which is characterized in that it can be used for both purposes. (6) In any one of claims 1 to 5, oxygen, an oxygen-containing mixed gas such as air, and nitrogen are added to the solution of the composite catalyst to form the oxygen 1() form. and propylene 1j (a method for synthesizing ace1, which is characterized in that the two are reacted). (7) In any one of claims 1 to 5, the solution of the composite complex is Impregnated and supported on a quality carrier,
A method for synthesizing acetone, which comprises passing an oxygen-containing mixed gas such as oxygen and air, and propylene through the mixture, and oxidizing the propylene with the bound oxygen in the oxygen complex. (8) In any one of claims 1 to 7, a basic (electron-fertile) compound such as sulfolane, dimethylsulfolane, dimethylsulfoxide, dimethylpolamide, etc. is added to the catalyst/8 liquid. or as a solvent for a composite catalyst.