JPS6039059B2 - Method for producing unsaturated ketones - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [1] (wherein X and x2 are both hydrogen atoms or one is a hydrogen atom, the other together with Z represents a single bond, and together represent a single bond or a hydrogen atom, a hydroxyl group, or a lower alkoxy group, R is a hydrogen atom or a lower alkyl group, and X3 and x4 are both hydrogen atoms or one of them is a hydrogen atom and the other represents a single bond together with Z2, Z2 represents a single bond together with X3 or X4, or is a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and R2 represents a hydrogen atom or a lower alkyl group, one of X5 and x6 is a hydrogen atom, the other together with Z represents a single bond, and n is 0 or 1). The present invention relates to a method for producing saturated ketones and/or Q.6-,6.go-unsaturated ketones. Q.3-,y.6-unsaturated ketone and Q.0-,6.go-unsaturated ketone (hereinafter referred to as unsaturated ketone [1]) represented by general formula [1] are themselves fragrances. It is a substance that is useful not only as a substance but also as an intermediate in the production of fragrances, medicines, agricultural chemicals, and various pigments. According to the present invention, propargyl represented by the general formula [D] (wherein X,, X2, X3, X4, R,, R2, O, Z and n have the same meanings as in the general formula [1]) type alcohol (hereinafter referred to as propargyl type alcohol)

Unsaturated ketone [1] can be produced by heating and isomerizing [0]. propargyl alcohol

[0] is the general formula [N] (wherein X,, X2, X3, X4, R,, R2, O, Z and n have the same meanings as in the general formula [1], and halo. A halogen compound (hereinafter referred to as a halogen compound [W]) represented by an atom) is mixed with mesityl oxide and/or imesityl oxide (hereinafter referred to as mesityl oxides) in the presence of an alkali condensate. General formula [m] (in the formula, X, .X2, X3, X4) obtained by reacting
, R,, R2, Z, Z and n have the same meanings as in general formula [1]) (hereinafter referred to as 8-y-unsaturated ketone [m] ) is easily produced by ethynylation reaction. In this condensation reaction between the halogen compound [W] and mesityl oxides, the general formula [V] (in the formula
, X3, X4, R,, R2, Z, Z and n are general formulas [
Q with the same meaning as those in 1]
・8 Monounsaturated ketone (hereinafter referred to as Q.3 monounsaturated ketone [V]) is co-produced, but Q.3 monounsaturated ketone [V] is produced by 3.y-unsaturated ketone [V]. Therefore, Q・B-unsaturated ketone [V] was obtained as a mochi product by the condensation reaction of halogen compound [W] and mesityl oxides. at least a portion of 8.y-unsaturated ketone [m
An additional amount of propargyl type alcohol [n] can be obtained by isomerizing it into ] and subjecting it to an ethynylation reaction. Also, in the ethynylation reaction of 3-y-unsaturated ketone [m], depending on the reaction conditions, Q-8 monounsaturated ketone [V] may be produced as a by-product. Saturated ketone [V] is also isomerized to 3-y-unsaturated ketone [m] if desired, and then subjected to cethynylation reaction to produce propargyl type alcohol.

It can be set to [0].
Preferred examples of the new propargyl alcohol [□] used in the method of the present invention include the following compounds. However, the following structural formula is not intended to specify the three-dimensional structure of the compound. 4-isobutenyl-3-methyl-1-octyne-3-ol 4-isoprobenyl-3,7-dimethyl-1-1 25 octyne-3-ol 4-isoprobenyl-3,7-dimethyl-1-octyne-6-en-3-ol 4-isoprobenyl-3, 7-dimethyl-1-octyne-7-en-3-ol 4-isoprobenyl-3,7-dimethyl-1nonine-6-en-3-ol 4-isoprobenyl-3,7,11-trimethylododecar-1-yn-3-ol 4-isoprobenyl 3,7,11-trimethyl-dodeca-1-yne-6,10-diene-3-ole-4-isoprobenyl-3,7,11-trimethyldodeca-1-yne-10
-en-3-ol 4-isobutenyl-3,7,11
-trimethyldodec-1-yn-6-en-3-ol 4-isoprobenyl-3,11-dimethyl-7-ethyltrideca-1-yne-6,11-dien-3-ol 4-isoprobenyl-3,7,11-trimethylde Decar-1-yne-3,11-diol 4-isoprobenyl-3,7,11-trimethyl-11-methoxide deca-1-yn-3-ol Among these propargyl alcohols, Y...the following general formula [Da] (The dotted line in the formula indicates that a double bond may be present at any of the indicated positions) is, for example, 130
It is particularly important because it is easily converted into pseudonyone, which is an intermediate in the production of sionones, by thermal isomerization in a temperature range of 200°C to 200°C. propargyl alcohol

Among [0], compounds that are not included in the above general formula [oa] are of course treated in the same manner as above to obtain corresponding chain Q.8-, y.6-unsaturated ketones and/or Q. 8-, 6-monounsaturated ketones are produced. The typical manufacturing method of terbenoid compounds conventionally used requires long reaction steps and C3
Since expensive diketene or inpropanyl ether is used as an extender, there is a problem in that the extender accounts for a large proportion of the manufacturing cost. According to the method of the present invention, a novel propargyl alcohol

As can be understood from the above explanation, by using [0], it is possible to produce a compound that is the same or similar to a compound produced by a conventional method with a shortened reaction process and at a low production cost. Next, the method of the present invention will be explained in more detail. In producing B.y monounsaturated ketone [m] by reacting a halogen compound [W] and mesityl oxides in the presence of an alkali condensing agent, a condensation reaction between an organic halogen compound and a ketone is performed. There are known methods for producing substituted ketones, such as the following methods: legs, legs and {C
} method can be used. Bad: A method of condensing an organic halogen compound and a ketone in the presence of an alkali amide in liquid ammonia (Japanese Patent Publication No. 40
-19091 and 40-22173). 'B': A method of reacting an organic halogen compound with a ketone in the presence of an alkaline condensing agent and an amine catalyst or a phosphonium catalyst in a non-aqueous system (see Tsubaki Publication No. 40-22251 and Tarukai Publication No. 50-96514. In Example 67, which shows an example of the reaction between prenyl chloride and mesityl oxide in the specification of Publication No. 40-22251, condensation occurred on the methyl group side of the ketone.
8-dimethyl-2,7 nonajen-4-one with a yield of 7
However, as a result of detailed reexamination of this example by the present inventors, the yield of 2,8-dimethyl-2,7 nonadien-4-one was about 5% at most, and the yield of 3-isopropylene The total yield of lidene-6-methyl-5-hepten-2-one and 3-isoprobenyl-6-methyl-5-hepten-2-one was 70% or more. ). {q: A method of reacting an organic halogen compound with a ketone in the presence of an alkali condensing agent and a catalyst (amine catalyst, quaternary ammonium salt catalyst, or phosphonium salt catalyst) in a water-containing system (JP-A-50137713 and Kaisho 50-1965
(See Publication No. 14). Among these methods, Tsukuda and 'C' methods are preferred as industrially applicable methods, and method 2 is particularly preferred. Comparing Method 'B' and Method {C}, in addition to the fact that Method 'B' generally has a lower reaction rate, it does not require the use of the alkaline condensing agent in its solid state, so it has problems with reproducibility of the reaction and the working environment. It has the advantage of being soothing. In carrying out the condensation reaction between the halogen compound [W]N and mesityl oxides, the same reaction conditions as in the above-mentioned known methods can be employed, but the preferred method Briefly, it is preferable to use sodium hydroxide or potassium hydroxide as the alkali condensing agent, and the amount used is from about equimolar to about 10 times the molar amount of the halogen compound [W]. Ranges are preferred, with about 1.3 tones to about 4 moles particularly preferred. As the catalyst, primary amines, secondary amines, tertiary amisos, salts of these amines, quaternary ammonium salts and phosphonium salts can be used, with quaternary ammonium salts and phosphonium salts being particularly preferred. Examples of recommended catalysts include tetrabutylammonium chloride, trimethylbenzylammonium chloride, trimethyllauryl ammonium chloride, trimethylcetylammonium chloride, trimethylstearylammonium chloride, trimethylstearylammonium chloride, dimethyldicyclohexylphosphonium chloride, and methyltricyclohexylphosphonium. Examples include chloride, ethyltricyclohexylphosphonium chloride, and ethyltricyclohexylphosphonium bromide. The amount of catalyst depends on the type of catalyst used, but it is generally about 0 relative to the amount of halogen compound [N] charged.
．． The range is from 0.001 mol% to about 20 mol%, preferably from about 0.0005 mol% to about 2 mol%. When employing the above method tC', it is preferable to supply the alkali condensing agent to the reaction system in the form of an aqueous solution, and the concentration of the alkali condensing agent in the aqueous solution of the alkali condensing agent is about 4% by weight to about 65% by weight. A range of up to In methods [B} and [C}, the reaction temperature is 000 to 100
The temperature can be arbitrarily selected within the range of 0.0 to 0.0, but from the viewpoint of reaction rate and selectivity, a temperature of about 20 degrees Celsius to about 7000 degrees Celsius is particularly preferable. The time required for the reaction varies depending on the type of catalyst, catalyst concentration, amount of alkali condensing agent, etc., but for example, when the amount of alkali condensing agent is about equimolar to the halogen compound [W], it takes about 10 to 3 hours, When the amount of the alkali condensing agent is about 1.5 to 4 times the mole of the halogen compound [W], the reaction is completed in about 1 to 1 field time. In the condensation reaction of halogen compounds [W] and mesityl oxides, Q.3-
An unsaturated ketone [V] is produced, but the two can be easily separated by precision distillation if desired. Then, this Q.8 monounsaturated ketone [V] is converted into an isomerization catalyst,
For example, when heated in the presence of an acidic catalyst, Q.8 monounsaturated ketone [V] is isomerized to a.y monounsaturated ketone [m]. Since 8-y-unsaturated ketone [m] has a lower boiling point than Q-8-unsaturated ketone [V], the mixture of both is called Q-B.
It is also possible to continuously extract only the 8·y-unsaturated ketone [m] by carrying out heating distillation under the isomerization reaction conditions of the -unsaturated ketone [V]. However, from the viewpoint of reaction efficiency, the production ratio of 8-unsaturated ketone [m]/Q-3-unsaturated ketone [V] is increased in the condensation reaction between halogen compound [W] and mesityl oxides. It is preferable. According to the research of the present inventors,
When the reaction temperature is high in the condensation reaction between the halogen compound [W] and mesityl oxides, or when the reaction is continued for a long time in the presence of an excess alkali condensing agent, the 8-y- Saturated ketone [m] is reverse isomerized to Q.8 monounsaturated ketone [V] in the system. For example, 5.0 moles of prenyl chloride and 10.0 moles of mesityl oxide are mixed with 24.2 moles of trimethylstearic ammonium chloride in a 55% aqueous solution of 7.5 moles of sodium hydroxide.
When the reaction is carried out at 32 to 35 mm in the presence of water, the reaction time is 1.
The conversion rate of prenyl chloride in 5 hours was 55% and 3
-isoprobenyl-6-methyl-5-hepten-2-one vs. 3-isof. The production ratio of lopylidene-6-methyl-5-hepten-2-one is 90:10, but 3. Immediately, the conversion rate of prenyl chloride was 84%, and the above production ratio was 78:22, and after 5 hours, the conversion rate of prenyl chloride was 93%, but the above production ratio was 78:22. It became seal 23. Therefore, stopping the condensation reaction when the conversion rate of the halogen compound [W] reaches about 70 to 80% is effective in increasing the reaction efficiency of the condensation reaction. In addition, when considering distillation separation after isomerization or distillation separation simultaneously with isomerization as an acidic catalyst when isomerizing Q.8 monounsaturated ketone [V] to B.y-unsaturated ketone [m], It is preferable to use an acid having a boiling point higher than that of the 8-y-unsaturated ketone [m], and examples of such acids include aliphatic or aromatic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and laurylsulfonic acid. sulfonic acid, p-toluic acid, 4-nitro m-toluic acid, 4-
monocyclic, aromatic or alicyclic monocarboxylic, dicarboxylic or polycarboxylic acids containing heteroatoms such as hydroxybenzoic acid, vanillic acid, 4-nitroisophthalic acid, cyclohexylcarboxylic acid, or adipic acid;
1. Saturated or unsaturated aliphatic or heteroaliphatic monocarboxylic acids, dicarboxylic acids that may be hydroxylated and/or phenyl-substituted, such as 2-dihydroxystearic acid, benzylic acid, p-nitromofuric acid, diglycolic acid Alternatively, polycarboxylic acids, aliphatic or aromatic amino acids such as indolebutyric acid and 1,2-diaminocyclohexanetetraacetic acid, or inorganic acids such as metaphosphoric acid and phenylposphinic acid may be mentioned. The isomerization temperature when using an acidic catalyst is about 80 oo to about 200 oo
Temperatures before midnight are preferred. Furthermore, when the isomerization reaction of Q.8 monounsaturated ketone [V] to 8.y-unsaturated ketone [m] is carried out under basic conditions, hydroxide (e.g. sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, etc.), alkali metal salts or alkali metal salts (such as sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, calcium carbonate, magnesium carbonate) etc.), alkali metal amides (
(e.g., lithium amide, sodium amide, potassium amide, etc.), alkali metal alcoholates (e.g., sodium methoxide, sodium ethoxide, sodium-t
en-butoxide, potassium-ten-butoxide, etc.)
, and organic nitrogen bases (e.g. triethylamine, triethylamine, triethylamine, 1,5-diazabicyclo-[3,4,
0]/nene-5,1,5-diazabicyclo[5,4,
0] undecene-5,2-dimethylamino-1-pyrroline, 1,4-diazabicyclo[2,2,2]octane,
Tertiary amines such as 5-methyl-1-azabicyclo[3,3,0]octane, hexamethylenetetramine, jetanolamine, secondary amines, cyclic imines, etc.). The isomerization temperature varies depending on the type and amount of the basic isomerizing agent used, and whether a non-aqueous or aqueous reaction form is used. When using similar metal salts, alkali metal amides, alkali metal alcoholates, etc., it is usually -10 ~
100°C is preferred, and if an organic nitrogen base is used, 1
00-2000C is preferable. What is the amount of basic isomerizing agent used?・Freely select from 1% to 400% by weight based on B-unsaturated ketone [V] depending on the isomerization rate, economic efficiency, type of isomerizing agent used, isomerization temperature, etc. be able to. Further, when the isomerization reaction is carried out in an aqueous solution using, for example, sodium hydroxide as the isomerization agent, the reaction rate can be increased by adding a phase transfer catalyst as a promoter. Examples of the phase transfer catalyst include amine catalysts, quaternary ammonium salts, and phosphonium salts employed in the condensation reaction between the halogen compound [W] and mesityl oxides. This means that Q.8-monounsaturated ketone [V] and/or 8.y-unsaturated ketone [m] obtained by the condensation reaction of halogen compound [N] and mesityl oxides.
From the mixture, 8.y monounsaturated ketone [m], which is a low boiling point substance, is extracted, and at the same time, it is a high boiling point substance. This means that by recycling the Q.8 monounsaturated ketone [V] to the condensation reaction system, the isomerization reaction can be carried out economically and efficiently. Furthermore, Q.
3-unsaturated ketone [V] vs. 8-y-unsaturated ketone [m]
Although the equilibrium composition ratio varies depending on the compound, it is approximately (85 to 55
) pairs range from (15 to 45). The 8-y-unsaturated ketone [m] thus obtained was prepared using a known method.
Propargyl-type alcohol is produced by ethynylation reaction.

It can be guided to [0]. Conventionally used ethynylation methods include the following methods. 'a': A method of ethynylation using a Gregnard reagent (in THF or other suitable solvent, ethynylmagnesium halide, which may be generated on the spot, is reacted with a ketone). 'b); A method of reacting acetylene with alkali metals such as sodium, potassium, calcium, or alkali metals in liquid ammonia to form acetylide, and reacting this with a ketone. 'c}; Reaction of acetylene and ketone in a polar solvent (e.g. N.N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc.) in the presence of a strong alkali metal compound such as potassium hydroxide, potassium alkoxide, sodium amide, etc. How to do it. {d}: A method in which acetylene and ketone are reacted in liquid ammonia in the presence of a catalytic amount of sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium alkoxide, or the like. Method 'a' can be used for small-scale synthesis, but is not suitable for large-scale operation. In method {b}, since a large amount of alkali is used, Q.8- from 8.y-unsaturated ketone [m] is
Accompanied by reverse isomerization to unsaturated ketone [V]. For example, if 69 parts of metallic sodium are present in 3 parts of liquid ammonia,
After blowing acetylene gas into this to form acetylide, 500 g of 3-isoprobenyl-6-methyl-5-hepten-2-one (99% purity) was added to carry out the ethynylation reaction. The composition of is 5% of 3-isoprobenyl-6-methyl-5-hepten-2-one, 3
-isopropylidene-6-methyl-5-heptene-2-
10%, 4-isoprobenyl-3,7-dimethyl-
The content of 1-octyne-3-ol was 85%. Method (c)
When the ethynylation reaction is carried out in the presence of a catalytic amount of alkali in However, considering problems such as production cost and post-treatment, the above-mentioned 'c' is the ethynylation method used in the present invention.
} and {d} methods are particularly preferred. (c} and'
When carrying out the ethynylation reaction by method d-, sodium hydroxide or allium hydroxide is used industrially.
・0.1 to 1% by weight based on y-unsaturated ketone [m]
, particularly preferably using 0.5 to 3% by weight at a reaction temperature of -5 to
It is best to carry out the process at a temperature of 5°C. The propargyl alcohol [n] thus obtained can undergo a rearrangement reaction by heating and be induced into an unsaturated ketone [1]. This rearrangement reaction can be carried out in either a liquid phase or a gas phase, and a reaction temperature of 100 to 400 oo can be used, but from the viewpoint of reaction rate, in the case of a liquid phase method, a temperature of 13
0 to 230 qo is preferable, and in the case of a gas phase method, 250 to 4000 qo is preferable, although it depends on the residence time. Although the reaction may be carried out in the atmosphere, it is usually preferable to carry out the reaction under an atmosphere of an inert gas such as nitrogen or helium.
There is no particular limitation on the reaction pressure, and the reaction can generally be sufficiently carried out under atmospheric pressure. However, propargyl alcohol

If the boiling point of [0] is lower than the reaction temperature used,
Alternatively, when employing a gas phase method, it is preferable to carry out the reaction under increased or reduced pressure that meets these conditions. Although the use of a solvent is not essential, any solvent that is stable under the rearrangement reaction conditions, does not participate in the reaction, or improves the selectivity may be used. For example, propargyl alcohol [
0], when 4-isoprobenyl-3,7-dimethyl-5-octyne-6-en-3-ol [ob] is reacted in a nitrogen stream at a reaction temperature of 150°C for 1 feeding time, 6,
10-dimethyl-3,5,9-undecatriene*2
-one [la] and 6,10-dimethyl-3,6,9
- About 3 lbs of a mixture of undecatrien-2-one [lb]
Obtained with a yield of 7%. This reaction is diagrammed below. The unsaturated ketones [la] and [lb] obtained in this way are useful as fragrances in themselves by cyclizing with phosphoric acid or sulfuric acid as a catalyst, and are useful in agricultural chemicals, pharmaceuticals, etc.
This can lead to ionones, which are important intermediates in the production of various pigments. This method solves the production cost problems of the CIaisen rearrangement reaction using diketene or the CIaisen rearrangement reaction using improbenyl ether, which have been the mainstream C3 extender in terbenoid synthesis for the past few decades. In addition, there are also advantages such as shortening of the reaction process, and the above-mentioned terbenoids can be produced industrially at low cost. Examples will be described in detail below. Example 1 To a solution of 600 qo of sodium hydroxide and 490 qo of water, 980 ml of mesityl oxide, 520 ml of prenyl chloride, and 25 ml of trimethylstearylammonium chloride were added, and a water bath reaction was carried out (the reaction temperature rose to 70 qo). The reaction was terminated after 2 hours. The reaction solution was poured into water, extracted with ether, washed with water, and dried. After removing the solvent under reduced pressure, the remaining 1,250 ml was distilled to recover excess mesityl oxide, and high-boiling substances such as 3-isoprobenyl-6-methyl-5-hebuten-2-one and 3-isoprobenyl-6-methyl-5-hebuten-2-one
A 2.5:1 mixture of isopropylidene-6-methyl-5-hepten-2-one was obtained (purity 96.4
%). The purity of prenyl chloride used was 83.71.
%, 3-isoprobenyl-6-methyl-
The yield of 5-hepten-2-one was 60%, and the yield of 3-isopropylidene-6-methyl-5-hepten-2-one was 24%. When the above mixture is distilled and separated using a precision distillation column with 30 theoretical plates, it has a bp of 32 to 3400 (0
．． 3-isoprobenyl-6-methyl-5-hepten-2-one was obtained from the fraction of 2 Yanagi Hiyoshi, bp 35-38q0.
(From the fraction of 0.2 days, 3-isopropylidene-6
-Methyl-5-hepten-2-one was obtained. These structures were confirmed by the following method. Infrared absorption spectrum (inhibition-1) 1714 (>C=○), 1642 (>C=C<), 14
45, 137 ships 135 in 115 in 900 nuclear magnetic resonance spectra (6 Iso SI4) 1-57, 1.58 each S, Kounichi, CH3-1.
99 s, 3 days, 2.03-2.40m, 2 days, 1 CH
2-3.07 t, IH, 4.85 4.89each s, 2 days,: CH2 infrared absorption spectrum (skin-1) 1688 (>C=0), 1615 (>C=C<), 1440, 1375 , 135
0, 127 & 1202, 1170, 975 935 8
50 nuclear magnetic resonance spectrum (6 saddle SI4) 1.62, 1
．． 70, 1.75each s, 12th, CH3-2.
05 s, 9th, 2.88 d, 2nd, 1C ratio - 4.97 t. IH, 4.95 t, IH, CH- The obtained 3-isopropylidene-6-methyl-5-hepten-2-one 130 days is the number of theoretical plates together with the trans-1,2-cyclohexanedicarboxylic acid of 7 days. Put it into the bottom of the 5th stage precision distillation column, the degree of vacuum is 30 days, and the reflux ratio is 3.
Distilled at 0/1 to obtain 107 pieces of crab matter. As a result of gas chromatography analysis, this product was found to be 3-isoprobenyl-6-methyl-5-hepten-2-one (
94%) 3-isopropylidene-6-methyl-5-hepten-2-one (6%). The following ethynylation reaction was carried out in combination with 410% of the above-mentioned 3-isoprobenyl-6-methyl-5-hepten-2-one. 5
After putting 3 ml of liquid ammonia into a 3-hole flask and adding 70 ml of metallic sodium, acetylene gas was blown into the flask. When the reaction solution turned gray, the blowing of acetylene gas was stopped, and 517 g of 3-isoprobenyl-6-methyl-5-hepten-2-one was added, followed by blowing acetylene gas and reacting for 3 hours. After removing ammonia, the mixture was neutralized with ammonium chloride, poured into water, and extracted with ether. After drying with glass powder, the solvent was removed under reduced pressure. A fraction of 524 fractions was distilled under reduced pressure to obtain a fraction of 519 fractions with a bp of 59 to 61° C. (0.5 fractions). This is 3-isoprobenyl-6-methyl-5-hepten-2-one (2%),
3-isopropylidene-6-methyl-5-heptene-2
-one (8%) and 4-isoprobenyl-3,7-dimethyl-1-octyne-6-en-3-ol (90%). The structure of the product was confirmed by the following method. Infrared absorption spectrum (Ka-1) 3440 (1OH), 3300, 2120, 1640,
1450, 137 & 112 & 1030, 900 nuclear magnetic resonance spectra (6 females) 1.40 s, 3 days, 1-60 S, Mother's Day, CH3-1.72, 1.73each s, Chihito, CH3-2.
00-2.47m, 9 days, 2.30 s, IH, 1C3CH-ca. 4.83-5.00m, 3 days, =CH-, =CH
2 then 4-isoprobenyl-3,7-dimethyl-1-
Octin-6-en-3-all 192 yen (purity 92.
3%) was placed in a three-necked flask of 500 ml and heated under a nitrogen atmosphere at an internal temperature of 150 q0 for 10 hours to carry out a rearrangement reaction. The reaction solution is vacuum distilled as it is to reduce the bp containing unreacted raw materials.
Low boiling point fraction 1 of ~76℃ (0.16-0.17 side)
01 and the rearrangement product 6,10-dimethyl-3,
bp76-9 consisting of 5,9-undecatrie-2-one and 6,10-dimethyl-3,6,9-undecatrien-2-one is o (0.16-0.17)
A high boiling point fraction of 70% (purity 94.7%) was obtained. The structure of the rearrangement product was determined by separating the resulting mixture into two components using dispersion gas chromatography, and the infrared absorption spectrum and nuclear magnetic resonance spectrum data for one component were obtained from commercially available 6,1
This coincides with those of 0-dimethyl-3,5,9-undecatrien-2-one, and furthermore, this compound was reacted with a phosphoric acid catalyst by a conventional method to obtain Q-ionone and B-ionone. , 6,10-dimethyl-3,5,9
-Undecatrien-2-one. The structure of the other component was determined by the following method: 6,10-dimethyl-3,
It was confirmed to be 6,9-undecatriene-2-one. Infrared absorption spectrum (arc-1) 3030, 1675, 162 pieces 1440, 1376,
1360, 1255, 983 842 nuclear magnetic resonance spectra (6 inseminations 14) 1.60 (S, sea bream), 2,11 (S, group), 2.72 (
m, Misaki), 5.01 (m, IH), 5.12 (m, IH
), 5.94 (m, IH), 6.40-6.90 (m,
IH) Examples 2 to 8 Various alkyl halides [W] and mesityl oxides are condensed under various conditions, and the by-produced Q.B-unsaturated ketone [V] may be 6.
The y-unsaturated ketone [m] is heated isomerized and distilled, and the obtained 8.y-unsaturated ketone is subjected to an ethynylation reaction under various conditions to produce propargyl alcohol.

It was set to [0]. Then, the corresponding unsaturated ketone [1] was obtained by carrying out a heating rearrangement reaction. The results are shown in Table 1. Example 9 100 g of 3-isopropylidene-6-methyl-5-hepten-2-one obtained according to the method of Example 1 was mixed into a solution of 142.4 g of sodium hydroxide and 145.5 g of water, and the reaction temperature was increased. The isomerization reaction was carried out at 70-75o0. Changes in the reaction solution over time were analyzed by gas chromatography, and the results are shown in Table 2. The reaction solution was extracted with n-hexane, washed with water, dried, and then the solvent was removed under reduced pressure, and the residue was crudely distilled to recover a distillate of 97.5%. This thing is gask. As a result of the chromatographic analysis, 3-isopropylidene-6-methyl-5-hepten-2-one vs. 3-isopropylidene-6-methyl-5-heptene-2
-The on ratio is 70. The inner seal was 39.3. This product was subjected to precision distillation to obtain 3-isoprobenyl-6-methyl-
5-hepten-2-one (purity 94.51%) at 27.
I got 4#. Table 1 16.6 hours of the obtained 3-isoprobenyl-6-methyl-5-hepten-2-one was added to an autoclave by introducing acetylene gas in the presence of a solution of 200 parts of liquid ammonia, 0.28 parts of potassium hydroxide, and 10 parts of ethanol. The reaction was carried out in grape at 0°C for 6 hours. After collecting ammonia and excess acetylene gas, the residue was neutralized with ammonium chloride, poured into water, extracted with ether, washed with water, and dried. After removing the solvent, the residue was crudely distilled under reduced pressure to obtain 15.
I got 9 nights. As a result of gas chromatography analysis of crab matter, 3-isoprobenyl-6-methyl-5-hepten-2-one, 3-isopropylidene-6-methyl-5-hepten-2-one, and 4-isoprobenyl-3,7 5. -dimethyl-1-octyne-6-en-3-ol, respectively. Government size 15. The branch size was included at a ratio of 76.2. Additionally, it contained 3.1% of 4-isopropylidene-3,7-dimethyl-1-octyne-6-en-3-ol as an impurity. Table 2 [Kono] In Examples 9 to 12, selectivity indicates the following. Selectivity (%) of (3-isoprobenyl type + 3-isopropylidene type) after reaction = (3-isoprobenyl type + 3-isopropylidene type) in raw materials x 100 Example 10 In the method of Example 9, 3-isopropylidene type When carrying out the isomerization reaction using 25.0 mm of 6-methyl-5-hepten-2-one, 0.257 mm of trimethylstearylammonium chloride was added as a phase transfer agent,
Table 3 shows the results obtained in a solution of 70 quarts of sodium hydroxide and 46 quarts of water. Table 3 Example 11 In carrying out the isomerization reaction in the method of Example 10 using 25.3 hours of 3-isopropylidene-6-methyl-5-hepten-2-one, the alkali concentration was lowered. The reaction was carried out at 4,000 ml of a solution of 12.5 ml of sodium hydroxide and 37 ml of water, with the addition of 0.24 ml of trimethylstearylammonium chloride as a phase transfer catalyst. The results are shown in the table. Table 4 Example 12 In carrying out the isomerization reaction using 3-isopropylidene-6-methyl-5-hepten-2-one in the method of Example 9, 1,
The reaction was carried out at 120q0 using 5-diazabicyclo[5,4,0]undecene-5 for 1.5 nights. Changes in the reaction solution over time were analyzed by gas chromatography, and the results are shown in Table 5. Table 5

Claims (1)

[Claims] 1 General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and X_2 are both hydrogen atoms, or one is a hydrogen atom and the other is combined with Z_1 represents a single bond, Z_1 together with X_1 or X_2 represents a single bond, or is a hydrogen atom, a hydroxyl group or a lower alkoxy group, R_1 is a hydrogen atom or a lower alkyl group, and X_3 and or one is a hydrogen atom and the other together with Z_2 represents a single bond, Z_2 is X_3
or together with X_4 represents a single bond or is a hydrogen atom, hydroxyl group or lower alkoxy group, and R_
2 is a hydrogen atom or a lower alkyl group, and n is 0 or 1) The general formula is characterized by thermal isomerization of propargyl alcohol ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula X_1, X_2, X_3, X_4, R_1, R
_2, Z_1, Z_2 and n have the same meanings as in formula [II], one of X_5 and X_6 is a hydrogen atom, and the other represents a single bond together with Z_3). A method for producing β-, γ/δ-unsaturated ketones and/or α/β-, δ/ε-unsaturated ketones. 2 General formula [VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and X_2 are both hydrogen atoms, or one is a hydrogen atom, and the other together with Z_1 represents a single bond, General formula [VII] ▲ characterized by thermally isomerizing a propargyl-type alcohol represented by (Z_1 together with X_1 or X_2 represents a single bond, or is a hydrogen atom, a hydroxyl group, or a lower alkoxy group) There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1, X_2, and Z_3 are as shown in formula [VI], one of X_5 and )
α・β-, γ・δ-unsaturated ketones and/
or the method for producing α/β-, δ/ε-unsaturated ketones according to claim 1. 3 Structural formula [VIII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IX] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula One of X_5 and X_6 is a hydrogen atom,
The other is α, β-, γ, δ-unsaturated ketone and/or α represented by (together with Z_3 represents a single bond)
・Claim 1 of β-, δ/ε-unsaturated ketones
Manufacturing method described in section. 4 General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and X_2 are both hydrogen atoms, or one is a hydrogen atom, and the other together with Z_1 represents a single bond, Z_1 together with X_1 or X_2 represents a single bond, or is a hydrogen atom, a hydroxyl group, or a lower alkoxy group, R_1 is a hydrogen atom or a lower alkyl group, and X_3 and X_4 are both hydrogen atoms, or One is a hydrogen atom, the other together with Z_2 represents a single bond, and Z_2 is X_
3 or X_4 together represents a single bond, or is a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and R
_2 is a hydrogen atom or a lower alkyl group, n is 0 or 1, and halo. is a halogen atom) is reacted with mesityl oxide and/or isomesityl oxide in the presence of an alkali condensing agent. General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X_1, X_2, X_3, X_4, R_1, R
By ethynylating the β/γ-unsaturated ketone represented by Yes▼ (in the formula X_1, X_2, X_3, X_4, R_1, R
_2, Z_1, Z_2 and n have the same meanings as those in formula [IV]) General formula [I] ▲ Numerical formula, chemical formula, table, characterized by heating and isomerizing this etc. ▼ (In the formula, X_1, X_2, X_3, X_4, R_1, R
_2, Z_1, Z_2 and n have the same meanings as in formula [IV], one of X_5 and X_6 is a hydrogen atom, and the other represents a single bond together with Z_3). A method for producing β-, γ/δ-unsaturated ketones and/or α/β-, δ/ε-unsaturated ketones. 5 General formula [X] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 and X_2 are both hydrogen atoms, or one is a hydrogen atom, and the other together with Z_1 represents a single bond, Z_1 together with X_1 or X_2 represents a single bond, or is a hydrogen atom, a hydroxyl group, or a lower alkoxy group, R_1 is a hydrogen atom or a lower alkyl group, and halo. is a halogen atom) General formula obtained by reacting a halogen compound with mesityl oxide and/or isomesityl oxide in the presence of an alkali condensing agent [XI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X_1, Z_1 is the formula [X
) with the same meaning as those in )
・By ethynylating a γ-unsaturated ketone, a general formula [XII] ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X_1, X_2, R_1 and Z_1 are the formula [X
The general formula [XIII] ▲ has mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, X_1, X_2, R_1 and Z_1 are the formula [X
] have the same meaning as those in
One of 6 is a hydrogen atom and the other together with Z_3 represents a single bond). The method for producing saturated ketones according to claim 4. 6 Structural formula [XIV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Structural formula [XV] obtained by reacting a halogen compound represented by with mesityl oxide and/or isomesityl oxide in the presence of an alkali condensing agent ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ By ethynylation reaction of β-γ-unsaturated ketone represented by , propargyl alcohol represented by the structural formula [VIII] There are general formulas [IX] ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by thermal isomerization of 5. The method for producing α·β-, γ·δ-unsaturated ketones and/or α·β-, δ·ε-unsaturated ketones represented by the following formula.