JPS58118537A - Novel acetophenone derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The acetophenone derivative of formulaI(R is group of formula II or III). EXAMPLE:m-(2-Hydroxy-2-propyl)-acetophenone. USE:Raw material of functional polymer, polymeric surface active agent, resin modifier, etc. PROCESS:The compound of formulaIcan be prepared by the demethylation of the substituted cumene hydroperoxide of formula V obtained by the liquid-phase oxidation of the substituted isopropylbenzene of formula IV in the presence of an iron salt catalyst at 0-100 deg.C under atmospheric pressure. When R of the resultant compound is group of formula II, the compound can be converted to another compound of formulaIwherein R is group of formula III by the dehydration at 0-350 deg.C in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 7-setophonone derivative, which is a useful intermediate in the fields of functional polymers, polymeric surfactants, resin modifiers, etc., and a method for producing the same. In the polymer industry, various highly responsive polymers have been developed, but the synthesis of raw material monomers is generally complicated. The current situation is that the price is also high.

In view of the current situation, the inventors of the present invention have conducted a thorough investigation and found that the synthesis method is much easier than that of the raw material monomers developed so far, and that it can be provided industrially advantageously. We have now discovered a new acetophenone derivative useful as a raw material for functional polymers.

(c) A novel acetophenone conductor represented by general formula (4), b) Demethylation of a substituted chimene hydroperoxide group represented by general formula (B) at 11 degrees from θ to /θθ°C in the presence of an iron salt catalyst. The method for producing a novel acetophenone derivative and the method for producing a compound represented by the general formula (0) shown in the present invention are not limited to the industrial method, but are The general manufacturing method is the general formula (
0) (wherein R is similar to the above and Pl) It can be obtained by liquid phase air oxidation of snow-melted isopropylbenzene. The compound represented by this general formula (0) does not necessarily have to be of am degree.・In the case of diisobrobylbenzene,
Examples of impurities include diisopropylbenzene monohydroberoxide, acetyl bovine hydroperoxide, (-
The presence of monohydroxy-provir) cumene, sodium halinate, etc. does not interfere with the present invention.◇ In the present invention, iron salts of compounds of the general formula The catalytic demethylation reaction is usually carried out using the general formula (1 mole of a compound of Bl, an iron salt of 0.0θ/~200%, preferably o,
If the amount of iron salt used is less than oi-1 times the mole, the reaction rate will be slow, and
Other carbinol II reactions due to side reactions are di(
Co-hydroxy-provir) is often produced, resulting in a dangerous disadvantage. Also, is it used? If you use more iron salts than S4I in molar quantities, the reaction rate will increase, but side reactions may result in the formation of diphenols, such as impropenylphenol, or the formation of a heavy fraction of phenol.It is not a good idea to use iron salts. As long as it is hydraulically soluble, any iron salt can be used.
? ! 1804. F・(NO3)訃1・otB, Go is an example of the addition of these iron salts. It is best to add it with your body. Furthermore, examples of organic solvents suitable for carrying out the reaction smoothly are benzene and toluene.

Although it is possible to use a water-insoluble organic solvent such as methyl isobutyl ketone, the reaction temperature is usually carried out in the range of 0°C to /θθ°C, but preferably in the range of 1θ°C to 9θ°C. ℃ range is selected.・If the reaction temperature is less than 0℃, the rate of one reaction f#i will be extremely slow, and if the temperature of one reaction exceeds /θθ℃, there will be many side reactions. .

The reaction pressure is 1. Usually, the reaction is carried out under atmospheric pressure.

It is also possible to carry out under reduced pressure.

The compound represented by the general formula (4) is precipitated as a solid from the reaction mixture, or if an organic solvent is used, the organic solvent in the oil layer is removed by a conventional method such as distillation, and then the bottom liquid is further distilled under reduced pressure. If you need a #1 degree that can be repeated.

1. For example, alcohol, benzene.

Toluene, ether, chloroform, or.

Highly pure white crystals can be obtained by recrystallizing from these mixed solvents. If an organic solvent is used in conjunction with the (,2-hydroxy-probyl)-acetolysis reaction, the organic solvent in the oil layer can be removed. In addition, the crude product of (-monohydroxy-propylene)-7 cetophenone, or its recrystallized product can be used. , solid acids, etc.), sulfuric acid, hydrochloric acid,
Examples include strongly acidic ion exchange I/# resin, relical aluminum, and activated alumina. It is also possible to use a mixture of these. The amount of acid catalyst used also differs depending on the type of dehydration reaction. is usually selected from θ, 000! to 3θθ, preferably θ, 00/-200 weight for 1 (-17" dorochyre-brobil) -7 tophenophenone. If the amount of θ, θM used is too small, the reaction rate will be low, and if too much 3θθ is used, the deterioration of the impropenylacetophenone produced will be extremely disadvantageous. The reaction pressure is usually atmospheric pressure, but reactive distillation is also possible under reduced pressure. Dehydration reactions can also be carried out in the lower, gas, or phase. Impropenylacetophenone can be separated from the reaction mixture into bedding by distillation. These demethylation and dehydration reactions can be carried out either batchwise or continuously. It is possible. Next, the present invention will be explained with reference to examples, but the scope of the present invention is not limited by these examples. -7 Preparation of cetophenone in a separable flask, 9% by weight of m
A methyl isobutyl ketone solution containing 4% by weight of m-diisopropylbenzene dihydroperoxide and -(,2-hydroxy-propyl)-propylene hydroperoxide was added to the t-/θθθ temperature and heated to 50°C. reached IO''GK.11 A ferrous sulfate aqueous solution/θθθpts in which 27F of formal sulfuric acid was dissolved was added, and the reaction was carried out at 10°C. At the end of the reaction, no hydroperoxide was present at all, and the reaction was completed. Neutralize and wash the liquid to check for methyl isobutyl ketone under reduced pressure, and further distill the resulting can under reduced pressure to obtain a distillate of /. Ta.

When this distillate was recrystallized using benzene as a solvent, white crystals appeared. ．． 2jE was obtained, and this crystal was confirmed to be m-(--hydroxy-propyl)-7cetophenone as a result of NMR spectroscopy and mass spectrometry. j
~jJ"c) Example - Production of m-impropenylacetophenone Example/Production of m-impropenylacetophenone using m-(-monohydroxycopeqbiru)-acetophenone obtained in Ensulfonic acid sowg was added to m-(--hydroxyl-1-probyl)-7cetophenone j OP K acid (p-) 7 and dehydration reaction was carried out at normal pressure/lθ°C/hour.
Subsequently, /θθ axis-distillation is performed, /J/”C;//
A transparent fraction 36 of θBHg was obtained. This transparent fraction was analyzed by NMR spectroscopy.

As a result of mass spectrometry analysis, 1m-impropenylacetophenone was confirmed as 90 (#! degree yy, z%
) Example 3 A reaction similar to Example 3 of Robenylacetophenone was carried out, and the bottom liquid after distillation removal of methyl isobutyl ketone containing rn-(J-hydroxy-probyl)-7cetophenone 6211 was carried out. Using this as a raw material, m-impropenyl 7cetophenone was produced in the same manner as in Example. as an acid
, 1spC vs. m-(--hydroxy-provir)7
Cetophenone θ, 1jt6] was added, and the temperature was reduced to normal pressure/re 0.
The dehydration reaction mixture was distilled at /θIIjLHg to obtain a clear fraction trty of 74θ to /−1°C.

As a result of NMR spectrum analysis and mass spectrum analysis, this transparent region was found to be m-impropenyl 7cetophenone. (Gentle [97,5 tatami]) Patent applicant Sumitomo Chemical Industries, Ltd.

Claims (1)

[Claims] (c) New vL7 cetophenone derivative represented by general formula (4). General formula (4) for demethylation with A&
The evening represented by