JPS5877853A - Preparation of benzophenone azine compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a synthetic intermediate of hydrazine, etc., economically, and extremely advantageously in an industrial scale, by reacting a benzophenone imine compound with molecular oxygen in the presence of copper halide and dissolved copper. CONSTITUTION:The objective compound of formula II can be prepared by reacting the benzophenone imine compound of formulaI(R<1> and R<2> are 1-10C ether, acyl, acyloxy, alkoxycarbonyl, etc.; m and n are 0-5) with molecular oxygen in the presence of a catalyst comprising a copper halide (e.g. cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, etc.) and dissolved copper derived from metallic copper, cuprous oxide, cupric oxide, copper carbonate or copper formate, at 60-300 deg.C, preferably 90-230 deg.C. The amount of the dissolved copper is 1.001-5, preferably <=1.3g-atom per 1g-atom of halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces benzophenone/
This invention relates to a novel method for producing 7-gins, characterized by using azines (hereinafter referred to as azines or a mixture with molten steel produced from formic acid steel).

Azines are extremely useful substances as reaction intermediates in the production of hydrazine, and an inexpensive production method is desired.

There are many known methods for producing the corresponding azines by oxidizing imines. The catalyst that is effective for oxidation is mainly halogenated steel.

JIK No. 1 chloride steel is used (U.S. Patent No. 287
No. 0206). Other than copper halide.

In the presence of excess pyridine, steel (11 halide methoxide (Japanese Patent Application Laid-open No. 53-14704
7), among the patents for the precipitation of copper salts in the production of azines by oxidizing imines in the presence of copper salts, including acetic acid steel and copper thiocyanide.

It has been disclosed that copper salts of cyanide steel are also effective in the reaction (patent publication No. 53-71045). It is also known that coordinated polymeric catalysts are effective in oxidizing imines (Japanese Patent Application Laid-Open No. 131987/1987).

All these methods have the disadvantage of using expensive copper salts in very high concentrations. Furthermore, when using a polymer catalyst coordinating steel ions, the adsorbed steel may elute during the first reaction, and the steel ions may not necessarily be completely re-adsorbed near the end of the fifth reaction, or monodentate pyridines may This method cannot be said to be industrially advantageous since it requires the use of a special resin with specific characteristics.

They also discovered that a very small amount of molten steel produced from formic acid steel is effective in oxidizing imines to 7-ginsine.
I completed it and filed a patent application in 1986-524.
12). On the following page, he discovered that the catalytic activity of copper genide was specifically enhanced in a catalyst system in which molten steel coexisted, which is effective for oxidizing imines to produce azines, and completed the present invention. It's arrived.

In other words, the present invention is based on the general formula;

Cycloaliphatic or aromatic hydrocarbon groups and ether groups, heptadyl groups, acyloxy groups, flukoxycarbonyl groups, carboxylic acid amide groups, disubstituted amino groups, halogen groups, hydroxy groups, nitro groups, mutually the same or different groups selected from the group consisting of cyano groups, or R1 and V together may represent a single bond or ring. Also, s m and n are O or 1
It is an integer of ~5. ) Be/Zophenoneimine 7 and molecular oxygen in the presence of a halogenated steel catalyst! Let me touch you.

General formula: (RI in formula (1), R1, m, and n are general formula (1
)) This is a method for producing benzophenoneazines characterized by coexisting molten steel produced from formic acid steel.

The imines of the present invention are those represented by the general formula (I), and specific examples include benzophenone imine, 2-. 5+, or 4-methylbenzophenonimine, 2-. 5- or 4-ethylbenzophenonimine, 2-, S-.

or 4- n- and/or 1so-propylbenzophenonimine, 2+,! -, or 4- n- and/or 1
so- and/or tert-butylbenzophenonimine, 2-. 3- or 4-7 methyl benzophenonimine, 2-. 3- or 4-decylbenzophenonimine,
2-. 3- or 4-methoxybenzophenonimine,
4-cyclohexylbenzophenonimine, 4-phenylbenzophenonimine, 2@4-dimethybenzophenonimine, 2,3-dimethylbenzophenonimine,
5.4-Dimethylbenzophenonimine, 2,4-diethylbenzophenonimine, 2,5-diethylbenzophenonimine, s,4-diethylbenzophenonimine.

2-Methyl-4-ethylbenzophenonimine.

2-Methyl-4-butylbenzophenonimine.

2.2-,! , ter, 4, 4' +, 2. S'
-, 2゜l-0 or 3,4'-dimethylbenzophenonimine, 2-. 3- or 4-coolbenzophenonimine, 2-cool-4-methylbenzophenonimine,
4-talol-4'-ethylbenzophenonimine, 4
, 4'-dichlorobenzophenone imine, 4-nitrobenzopheno/imine.

2,4-cinitrobenzophenone i:/,4-human axybe/sophenone imine 7.4-N,N-dimethylaminobenzophenone imine, 4-acetylbenzophenone imine, 4-methoxycarbonylbenzophenone imine, 4-N , N-dimethylbenzophenone imine.

4-Cyanobenzophenone imi7. Examples include fluoreno/imine, xa/tonimine, 7thronimine, 7cridonimine, and the like.

Although the imino compound II)K used in the present invention is specifically illustrated, it goes without saying that other imines are also included. Methods for producing these imines include, for example, a method in which the corresponding benzophenones are reacted with ammonia, a method in which arylmagnesium bromide, which is a Grignyl reagent, is reacted with benzene/dinitriles, and dehydration with diarylamino alcohol. Imines obtained by any of these methods can be used in this reaction.

The imines used in the present invention are benzophenone and other various substituents or penzophenone in which substituents are combined to form a single bond or ring,
For industrial implementation, economically advantageous imines are preferably benzophenone imines in which m and n are 0 and benzophenone imines having 1.2 mono- or di-substituents.

l) What is rogogenated steel used in the present invention?

Cuprous chloride, cupric chloride, cupric bromide, cupric bromide, cupric iodide, cupric iodide, cupric oxychloride, cupric oxybromide, methoxychloride Examples include cupric methoxy bromide and cupric methoxy iodide.

In the present invention, as a method for preparing molten steel prior to making it coexist with halogenated steel, various methods previously proposed by Terumyo et al. (Japanese Patent Application No. 55-526
12). In addition, when preparing molten copper, even if undissolved raw materials remain, it is not necessary to remove the undissolved materials from the reaction system, and it is possible to add halogenated steel and molten copper raw materials at the same time. The amount of molten steel to be used in coexistence with halogenated steel is usually such that the number of Durham atoms in the total molten steel (including molten steel as halogenated steel) per 1 gram atom of halogen is 1.001 to 5. Preferably 2 or less.

More preferably, the amount is 1.3 or less.

The reaction conditions for the oxidation reaction of the present invention cannot be uniformly defined depending on the activity of the catalyst and the type of reaction, but the reaction temperature is 60 to 300°C, preferably 70 to 250°C, and more preferably 90 to 230°C. . The reaction time depends on the activity of the catalyst,
It is usually in the range of 0.1 to several hours, although it depends on the desired conversion rate and the like.

As molecular oxygen, oxygen gas alone may be supplied to the reaction system, or a mixed gas containing an inert gas such as nitrogen and oxygen gas, such as air, may be used.The pressure may be reduced or normal pressure. However, there are no particular restrictions on pressurization, but when using oxygen gas alone, it is 1 to 20 atm, and when using air, it is 1 to 40 atm.
Atmospheric pressure is appropriate.

The method of supplying oxygen gas or a mixed gas containing oxygen gas to the reaction system may be either a flow type or a closed type, but a blow flow type is preferable in order to suppress hydrolysis of imines by reaction product water. , l! It is preferable to use dry oxygen gas or a mixed gas containing oxygen gas.

Also, the reaction method can be either a batch method or a continuous method.
In order to improve the reaction rate, a multi-stage continuous method or the like may be selected as appropriate.In the present invention, a solvent is not required for 41. but.

To help dissolve the azines produced by the reaction and to maintain the reaction system in a solution state, a solvent may be added. S* helps dissolve 77 mooxides of benzenes and imines, which are products that are difficult to oxidize, and are especially poorly miscible with water and have low viscosity. preferable. For example, benzene, toluet/.

o-, at--, p-xylene, ethylbenzene.

Mesitylene, cumene, punidocume/, 7 milbenzene, aromatic saturated aspect ratio hydrogen having 6 to 16 carbon atoms and mixtures thereof, chlorbe/ze' I O1m -, p-dichlorobenzene, nitrobenzea.

0-, m-, p-dichlorunzene, o-, m-
0p-altoluene, diphenyl, phenanthrene,
7 Nisole, diphenyl ether.

Acetophenone, benzyl, benzophenone.

Examples include hexane, heptane, cyclohexane, cyclooctane, ethylcyclohexane, ethylene dichloride, tetrachlorethylene, diisopropyl ether, dipropyl ether, diyne butyl ketone, butyl acetate, butyl benzoate, phenyl benzoate, dimethyl phthalate, and the like. In the present invention, it is preferable to use an imination reaction solution of benzophenones as the imine. In this case, since the unreacted penzophenones act as a solvent, it is not necessarily necessary to add a solvent.

By coexisting demolition, the activity of halogenated steel can be significantly increased. Moreover, it is at least 4 to 5 times higher than the sum of the activity of wrinkle catalyst steel, making it extremely unique.

Since the catalyst system thus has remarkable high activity and high selectivity, it is possible to reduce the amount of catalyst used and shorten the reaction time compared to the case where halogenated steel is used alone. Along with this, there are advantages such as a reduction in oxidation reaction costs and a reduction in the burden of separation, recovery, and regeneration of the catalyst, making it an industrially extremely advantageous method for producing Asian products.

Hereinafter, a different explanation will be given with reference to Examples.

Example 1 Be/sophenone imine solution (benzo7enes i725.
8% by weight, the rest being benzophenone) 5011 (imine)
59,4i mol) was charged into a reactor and heated to 140'i:: while passing nitrogen through the bottom of the reactor at a rate of 20071'lHn. Catalyst and acidic acid steel (Co(HCOO)z・2H0) (manufactured by Wako Junkei) 10.719 (0,056 mmol) and No. 1 steel chloride (manufactured by Wako Junkei) 50.4q (o, 5
After adding 0.09 mmol), the reaction was carried out by stirring at 1401 n°C for 30 minutes under normal pressure while passing element a at a rate of 250 mm/l (molten steel 12110).
ppm).

Gas chromatography analysis of the reaction solution revealed that benzophenone azine was produced in a yield of 92% (18, 11 moles).

Comparative example 1 Chlorinated No. 1 steel with catalyst 50,41R9 (0,5094
1. C molten steel (1.080 ppm) subjected to exactly the same operation as in Example 1. The reaction was carried out for 30 minutes, but the yield of be/siphenonazine was 4.
% (0.8 mmol).

Comparative Example 2 Copper formate (Cu()ICOO)*2HtO11 as a catalyst
The same operation as in Example 1 was carried out except that 0,7119 (0,056 mmol) was added (molten steel 12
0 ppm). The reaction was carried out for 300 minutes, and the yield of takabe/siphenonazine was 15% (3.0 mmol).

Example 2 The same operation as in Example 1 was performed except that the reaction temperature was 120°C. When the reaction was carried out for 45 minutes, benzophenone 7 dine was produced in a yield of 89% (17,jj mol).

Example 3 The same procedure as in Example 1 was carried out, except that 5.4 μm (3,028 mmol) of copper formate and 25.2 μm (0°254 mmol) of steel chloride were added as catalysts.

When the reaction was carried out for 0 minutes with SO, benzophenone azine was produced in a yield of 36% (7.1 mlJ mol) (molten steel 6.OOppm) - Example 4 The same procedure was carried out except that air was used instead of oxygen. Exactly the same operation as in Example 1 was performed. When the reaction was carried out for 900 minutes, the yield of benzophenone/azine was as follows.

It was 90% (17.7 mmol).

Example 5 Benzophenone imine solution (Benzophenone imine 23
．． 8% by weight, the rest being benzophenone) 1oo & (imine 131-5j somol) was charged into a glass autoclave, and nitrogen was introduced from the bottom of the autoclave at 500117/i
It was heated to 140° C. while passing at a rate of y+in.

Copper formate as catalyst 17.9■ (Q, 094 mmol)
After adding 94.24 (0-851 jlJ mol) of cuprous chloride and cuprous chloride, air was blown into I N//r under a pressure of 4-G.
The reaction was carried out by stirring at 140° C. for 30 minutes while passing at a rate of 10 min.

Benzophenone 7-dine tfi yield S 1.0% (20i
9 mok) (@Steel decomposition 600 ppm) #
Example 6 Benzophenone imine solution (benzo7e/imine 23
．． 8% by weight, remaining benzophenone) 40II (imine)
52-6 mmol) and commercially available metallic copper powder (manufactured by Wako Junkei) 1
．． 5ν was charged into the reactor and heated at 140°C under normal pressure while passing nitrogen gas from the bottom of the reactor at a rate of 1004In.
Stirred for 1 hour. Thereafter, the copper powder was separated from the reaction solution using a glass filter (filter size Q-4). At this point, when liquid F was analyzed using a gas chromatograph, a very small amount (yield of 0.1% or less) of benzophenone azine was produced, and when the molten steel was analyzed using a colorimetric analysis, 6
It was 0 ppm.

Next, the furnace liquid 5ON was returned to the reactor, and cuprous chloride 55,
After adding 5 m1I (0,538 m!7 mol), exactly the same operation as in Example 1 was carried out (molten steel 1,200
ppm). When the reaction was carried out for 300 minutes, benzophenone 7 dine was produced in a yield of 45% (8.9 mmol).

Example 7 The same operation as in Example 6 was performed except that commercially available suboxide steel (manufactured by Wako Pure Chemical Industries, Ltd.) 1.0 & was used.

A v liquid containing 118 ppm of molten steel was obtained.

Next, 30 ml of KfP' liquid was returned to the reactor, and after adding cuprous chloride 50.5M9 (0,510 mmol),
Exactly the same operation as in Example 1 was performed (molten steel 1.20
When the reaction was carried out for 500 minutes, benzophenone 7 dine was produced in a yield of 91% (17.94 lmol).

Example 8 Benzophenone imine liquid C Benzophenone imine 25
8% by weight, *ribenzophenono) aOy and commercially available oxidation #
I2 Steel C Wako Pure Chemical Pure Chemicals 0゜1y was charged into a reactor and heated at normal pressure while passing nitrogen gas from the bottom of the reactor at a rate of 100"/fnh. When the liquid temperature reached 140°C, nitrogen was added to the reactor. The mixture was stirred for 20 minutes while the gas was stopped and hydrogen was blown in at a rate of 1,001 I4 (rIin).

After that, use a glass filter (filter size G-4).
) K was used to separate solids from the reaction solution.

The molten steel in this V liquid was 180 ppm, and a very small amount (yield of 0.1% or less) of benzophenone 7 zine was produced.

Next, return the KF solution to the reaction solution and add No.1 steel chloride.47.
After adding 7 Da (0,481 mmol), exactly the same operation as in Example 1 was carried out (molten steel 1.200 ppm)
When the reaction was carried out for sS minutes, 32% (6.5 mmol) of be/siphenonazine was produced.

Example 9 4-methylbenzophenone imine solution (20.0% by weight of 4-methylbenzophenone imine.

Remaining 4-methylbenzophenone) 50M (Imi73
The same procedure as in Example 1 was performed except that 0.9 mmol) was used. When the reaction was carried out for 30 minutes, 4
, 4'-dimethylbenzophenone azine yield 91%
(14.1 mmol) was produced.

Example 10 Copper formate as catalyst 10.7■ (0,056 mmol)
and cuprous bromide (manufactured by Kanto Katei) 73.2 da (0,50
The operation was exactly the same as in Example 1 except that 9 mmol) was added (molten steel 1,200 ppm),
When the reaction was carried out for 30 minutes, benzophenone azine was produced in a yield of 62% (122 mmol).

Comparative Example 3 The same operation as in Example 1 was carried out, except that No. 1 steel bromide 73,2IQ (0,509 mmol) was added as a catalyst (dissolved copper 1, 080 ppm). The reaction was carried out for 50 minutes, but the yield of benzophenone 7:) was 0.
．． 8% (0.16 mmol).

Example 11 Copper formate as catalyst 14. Exactly the same operation as in Example 1 was carried out (molten steel 1.220 ppm) except that D■ (0-(173 mmol)) and cuprous iodide 96-OH2 (0°5 oas remole) were added (molten steel 1.220 ppm) for 50 minutes. When the reaction was carried out, the yield of benzophenone azine was 74% (
14.6j mol).

Comparative Example 4 The same operation as in Example 1 was carried out except that 96.0 μm (0,504 mmol) of iodized No. 1 steel was added as a catalyst (molten steel: 1067 ppm).

The reaction was carried out for 30 minutes, and be/siphenone 7dine was produced in a yield of 0.2% (0.04j IJ mol).

Comparative Example 5 The same operation as in Example 1 was carried out, except that 14.0 μm (0,073,511 mol) of formic acid steel was added as a catalyst (molten steel: 156 ppm).

Although the reaction was carried out for 50 minutes,
The fi concentration was 2s% (4.5 mmol).

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano

Claims (1)

[Claims] General: In (Formula 11), at and R1 are a chain formula having 1 to 10 carbon atoms. Ether groups consisting of cycloaliphatic or aromatic hydrocarbon groups and wrinkled hydrocarbon groups, acyl groups, acyloxy groups, flukoxycarbonyl groups, carboxylic acid 7-mido groups, disubstituted amine-7 groups, and halogen groups, human a-oxy The same or different groups selected from the group consisting of a nitoxy group, a nitoxy group, and a cyano group, or RI and P may be combined to represent a single bond or ring. Moreover, m1 port is 0 or an integer from 1 to 5. ) and molecular oxygen are brought into contact with molecular oxygen in the presence of a copper halide catalyst, and the general formula:
) is a method for producing benzophenoneazines characterized by the coexistence of molten steel produced from copper formate.