JPS5813538A - Preparation of cyclic ketone - Google Patents

Abstract

PURPOSE:To prepare the titled substance, selectively, in high yield, under mild reaction conditions, by using a specific selenium compound or arsenic compound as a catalyst for the decomposition reaction of an alicyclic hydrocarbon hydroperoxide compound. CONSTITUTION:The objective compound is prepared by decomposing an alicyclic hydrocarbon hydroperoxide compound such as cyclohexyl hydroperoxide at 0- 160 deg.C, preferably 20-120 deg.C in the presence of a catalyst comprising a selenium compound selected from an oxyacid of selenium or an aromatic seleninic acid (e.g. phenylseleninic acid, 4-methoxyphenylseleninic acid, etc.) or an arsenic compound selected from an oxyacid of arsenic and an aromatic arsonic acid (e.g. phenylarsonic acid, hydroxyphenylarsonic acid, etc.). Combination of a small amount of a base with the above catalyst further improves the selectivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing lI-like ketone O, and more particularly to a method for producing concentrated ketone O, which consists of decomposing hydroperoxide compounds of monolithic hydrocarbons. .

It is widely known that when hydroperoxide compounds are decomposed in the presence of metal salts, aldehydes or ketones, and carlinic acid in alcohols are produced. Furthermore, when a hydroperoxide compound is decomposed in the presence of an alkali, a large amount of KaO heavy metals and aldehydes are produced, and when it is decomposed in the presence of nonacid O, mainly polymers are produced. Are known.

Decomposing hydroperoxide compounds in this way
Although it is already known that ketones or aldehydes are partially produced, there is still no known method to selectively obtain ketones or aldehydes in high yields by controlling the decomposition mechanism of hydroperoxide compounds. teichi'&i.

The present invention provides a method for converting certain compounds into cytocompounds O
By being present as a catalyst in the decomposition reaction system, the decomposition reaction proceeds even under mild reaction conditions, and when an alicyclic hydrocarbon hydroperoxide compound is used as the starting material hydroperoxide compound, 0 selectively,
This method was completed based on the finding that a reward ketone can be produced in high yield.

In the method for producing cyclic ketones of the present invention, catalyst a, (1) seley, which is used to guide the decomposition reaction of human peroxides of fat-concentrated hydrocarbons to the production of cyclic ketones with high selectivity;
It is different from o-oxyacid and aromatic selenic acid, and is a 97-sine compound, and 4 or Q) is an arsenic compound selected from arsenic, O-oxy-shun, and aromatic group arsonic acid.

As mentioned above, the catalyst used in the present invention is a specific O-hydrogen compound or arsenic compound.
The reviews are quite different.

Among the selenium compounds used in the present invention, examples of the seleyO oxyacid include selenic acid and selenite, but selenite is preferred from a practical point of view.

Aromatic seleenoic acid is a chemical compound represented by the general formula Examples of group-based seleenoic acids include Du, phenyl seleenoic acid, and 4-methoxy V.
7-ethyl lucele acid, 3-methota 7-eth! Lucelite acid, 4-methylferceleenoic acid, 8-fifluae=. V = Chive, 4-work N,,, Tsue = ni Yatun L l
-1-57a el selenic acid, 4-2F 4 fer selenic acid, 3-nitroa el selenic acid, snow-ditogastric 7 enyl heptalenic acid, z&-y el 7 el selenin II, 2.4- Shinito 7k xh*v 2in II
Examples of compounds in which the oxyacid of polystyrene, benzene, and selenium are bonded are 24,6-drimethylferceleene and the following formula.

Selenium compounds such as selenium oxyacids and aromatic selenium compounds as described above, which produce selenium oxyacids and aromatic selenic acids in the reaction system used in the present invention, etc. Zero-containing materials can also be used. Examples of such compounds. □, □, roar, cm2. □□O, 工, ,':l','I1. ．． ．． I l Selenium oxide (lIeOl) is a diphenyl dihydrogen which produces aromatic selenic acids when it comes into contact with human peroxide compounds. #4 Disarinids such as &/nolls (J, D, McCullo
sxghamd 11.8. Gowlsl, J.
Mutm, Chem, l1oc,, 71,
@74 (1 meeting 49) K is mentioned).

Among the arsenic compounds used in the present invention, examples of arsenic acid include arsenite, pyroarsenite, metaarsenite, nitric acid, biarsenic acid, and metaarsenic acid. be able to.

Aromatic arsonic acid general formula % formula %) (X
Examples of aromatic arsonic acids include phenylarsonic acid and diphenylarsonic acid. A metal compound 0-AI (OK) in which benzene 11 of polystyrene having a nine-dimensional formula is supplied with arsenic O oxy acid.

4 can be used.

Furthermore, even if the arsenic compound is other than the arsenic oxyacid and the aromatic arsonic acid as mentioned above, as long as the arsenic oxyacid and the aromatic arsonic acid are produced in the reaction system used in the present invention, etc. Compound 1 can be used for example with dihydric trioxide.

The selenium compound to be present in the reaction system used in the present invention is the amount of arsenic compound in a catalytic amount, that is, the molar ratio of 1-(LO61 twice, preferably 0.
1-5L01 times. Increasing the amount of catalyst by 1 times, i.e. equimolar, did not improve the effect; on the other hand, (
If it is less than 1 times LOOI, it will not exhibit sufficient catalytic effect.

When a selenium compound 1 and an arsenic compound are present as a catalyst, it is desirable to coexist with a small amount of a base.The addition of this base accelerates the decomposition of the do-tetraperiocytide metal. , the selectivity for ketogenesis is further improved.

If the 4IK catalyst is insoluble or sparingly soluble in the reaction wave containing the human-peroxide compound, the effect of the addition of base will be greater. Examples of bases include nitrogen-containing compound 1
For example, pyridine and the like, and alkali metal salts of cardic acid 2, such as sodium acetate, can be mentioned. The amount of such base extravasation is generally 100-001 times II! relative to the human peroxide compound. The amount within the range is selected.

The reaction temperature of the reaction used in the present invention, that is, the temperature of the human peroxide compound, is 180℃, or the temperature in the range of 20 to 120℃ is required. At temperatures lower than 160°C, the reaction rate of the hydroperoxide compound decomposition reaction is significantly reduced.

Therefore, it is not practical.

The present invention is a hydroperoxide compound of an alicyclic hydrocarbon), and by a selective decomposition reaction.
The resulting product is a cyclic ketone. A chemical compound obtained from alicyclic hydrocarbons by contacting them with peroxides or oxygen in an active state.

It is a self-weighting metal that can be represented by the following general formula (which may contain any substituent, as long as it does not interfere with the two-fold reaction). Regarding the number of carbon atoms contained in the hydrocarbon 111Kt that forms the alicyclic hydrocarbon group, there is no limit to q# as long as the skeleton hydrocarbon bulk III exists stably, but generally a 3- to 2-membered q# is used. , preferably S to 18-membered lIO.

Hydroperoxide compounds of alicyclic hydrocarbons can be obtained by oxidizing hydroperoxide compounds of alicyclic hydrocarbons with a large amount of peroxide. Examples of such oxidation methods include Mu, G., Davi@s, et al.

J, Chew, 1ioc,, 111! I8.
1941: D, L Vanllcklq,
etsl,, J, AIm, Chew, 8o
c,, 87.4144 (Is@!I) :C,W
, Jeffford & C.G., Liambat*
mouth.

〒*1rak*5ireaL*ttar4 zz, 1
111 (1881) K.

Examples of raw materials of the present invention include cyclohexyl hydroperoxide, citalohexel and doperyl hydroperoxide, Schiff-bentyl hydroperoxide, diterpentenyl hydroperoxide, cyclooctyl hydroperoxide, great peroxide,
Citalooctenyl hydroperoxide, tetra9yl hydroperoxide.

It is possible to list the four perios of dodecyl chloride.

The cyclic ketone obtained by the method of the present invention is a metal compound represented by the following general formula, and specific examples include diterhexanone, heclohexenone, citalopentanone, cyclobentenone, and cyclooctanone.

Mention may be made of Schiftetraoctenone, tetralon, and cyclododecanone.

According to the VSO method of the present invention, the oxygen selectivity to cyclic ketones is very high in the case of decomposing alicyclic hydrocarbons into cyclic ketones. When a hydrocarbon O peroxide compound of formula O is used as a raw material, the selectivity (yield of the reward ketone) is about 85 or more. Therefore, it can be used as a useful method for producing the main active WR#i concentrated ketone.

Examples of the present invention are shown in each case.

[Example 1] Phenylselenic acid O, ossr (AS) was added to a solution of cyclohexylhydroperoxy) Q, 5IIf in citalohexane NO9Kmk, and the mixture was heated to 40°C at 81°C. A fractionation reaction was carried out.9 When the reaction was stopped, the dotetraperoxide was completely decomposed into Schifta hexyl.A gas chromatograph analysis of the product in the decomposition reaction chamber revealed that the hexanone 0.44F (4, 5F
Rimol) and Shijaw e? /-eo, o s S t
The formation of (0,3Is electrolymole) was confirmed. The yield (selectivity) of cyclohexanone is so.

[Example 3] Cyclohexylhydroperoxy)'0.58f(t.
Dissolve 1ml of cyclohexane (1ml) in 50f of cyclohexane.
, diarsenic trioxide (5s, O,) 0. C15f'(
(L' in mol) and 0.4f of pyridine (1G<limole) were added, and the reaction was carried out at 81t for 6 hours.

When the reaction is stopped, cyclohexyl hydroperoxide is completely decomposed. The products in the decomposition reaction solution are
- Analyze by v Thorn 27 and return to 9 results 1 Non 0.
42f-(4.3 millimeters) and Shiku-a Hekinano-80,
05? (0,501 lmol) was produced. The yield (selectivity) of cycloxanone was 86.
・Pa゛'□゛1 [Example 3] Dissolved INK of cyclohexyl hydroperoxide 058f (10 mmol) in Schifte hequinane 5otK*, selenite (xseos) 0.1) 81F (0,819
mol) and pyridine (0.4F) were added, and the reaction was carried out at 81C for 150 minutes. At the time of termination of the reaction, Ducyclohexylhydroperoxide had completely decomposed. The products in the decomposition reaction solution were analyzed by gas chromatography, and the results showed that cyclohexanone (L4 mF (44 lmol) and V clohexanol O,OS f (Q, +
$ 0 # 174) O formation was confirmed. The yield (selectivity) of cyclohequinanone was 88.

- [Example 4] 5 of citalohexane (801 mol) was charged into a glass autoclave, and an oxygen oxidation reaction was carried out at 100 tons for 4 min. ) #cytalohexeno:n & 41F (4,1 mmol), ci, su, ritoheki 7 no io, s iF (134 s7l) and cyclohexene oxide 8.27F (!1Ij94l)
An oxidation reaction solution containing 9' was obtained.

Diphenyl diselenide (ph-li) was added to the above 0-oxidation reaction solution.
@-s・-Pk) 0.1@f (0.51 mmol) was added, and the reaction was carried out at 83° C. for 3 hours. At the end of the reaction, 9γ% of cyclohexenyl hydroperoxide was decomposed into a circle. As a result of analyzing the products in the decomposition reaction solution using a gas chromatography-V graph, it was found that cyclohexenone toor (4
y, s mmol), cyclohexenol 0.1? F(&
9?9 mol) and cyclohexene oxide O; 291
(3, Oi mmol) can be confirmed, and the yield (selectivity) of cyclohexenone is based on the cyclohexenyl hydroperoxide in the oxidation reaction solution, and the amount of vh cyclohexenone present in the oxidation reaction solution is (destroys nine quantities)
86%.

[Example 5] Cyclohexene oxidation reaction solution used in Example 4 and 11i1
-tJWIl conversion R response tIS OPK phenylselenic acid (kl) and pyridine o, x o
t (LISt94#) and lsO in SSC.
The reaction was carried out for minutes. When the reaction was stopped, 96% of the cyclohexenyl hydroperoxide was decomposed.

The products in the decomposition reaction solution were analyzed by gas chromatography, and the results showed that 4.8 f (S & Kaiden 9)
The presence of cenol 0*11 (tst trimol) and Schiff tetrahexey oxide 0111f (291' mol) was confirmed.

The yield of cyclohexenone (selectivity, calculated in the same manner as in Example 4) was 92%.

[Example 6] 40.4 f (593 F 9 mol) of cyclopentene was charged into a glass autoclave and heated with air at 82°C for 12
The oxidation reaction was carried out for 0 minutes, and cyclopentenylhydroperoxy)'3.58f (3!LSI mol), cyclobentenone 0.082F (1,Of 9 mol), cyclobentenol 0.3?11F (4, 5 electric!
An oxidation reaction solution containing mol) was obtained.

The above O oxidation reaction solution was added to phenylseleenoic acid (LIS・f(
0, tofurimor) and pyridine o, x4xt (1711
49 mol) was added thereto, and the reaction was carried out at SO 0 C for 181) minutes. At the time of termination of the reaction, Schiff-pentenyl hydroperoxide was completely decomposed, and the products in the decomposition reaction solution were analyzed using a Gascomadrogram 7, and the results showed that Schiff-pentenyl hydroperoxide (3 moles, 19 moles) and Schiff-pentynol were detected. The presence of cyto0.13F (3 LIt mol) in the citalobentene solution can be confirmed.

The yield of cyclobentenone (selectivity, calculated in the same manner as in Example 4) was 89.

Patent original person Koki Ube Co., Ltd. Agent: Patent attorney Yasuo Yanagawa

Claims (1)

[Claims] A hydroperoxide compound of the quantitative formula hydrogen chloride. A cyclic compound which is intended to be decomposed in the presence of a selenium compound selected from selenium oxyacids and aromatic selenic acids, or an arsenic compound selected from aW*O oxyacids and %book-based arunonic acids. How to prepare ketones.