METHOD FOR PRODUCING ALPHA-ALLYLATED CYCLOALKANONE

Abstract

Provided is a method with which an α-allylated cycloalkanone is obtained from a cyclic compound cycloalkanone used as a starting material. The method is a method for producing an α-allylated cycloalkanone represented by General Formula (III), and the method includes: a step 1: reacting a compound represented by General Formula (I) and alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent; and a step 2: reacting a crude product obtained in the step 1 and a compound represented by General Formula (II) in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by General Formula (III). The step 1 and the step 2 are consecutively performed. In the formulae above, the group -A.sup.1- (it should be noted that the front bond refers to a bond that binds to the carbon atom C.sup.1 and the back bond refers to a bond that binds to the carbon atom C.sup.2) is an alkylene group having 4 or more and 20 or less of carbon atoms that optionally contains a hetero atom and optionally has a substituent, and R.sup.4 is a hydrogen atom or an alkyl group having 1 or more and 4 or less of carbon atoms.

Claims

1: A method for producing an α-allylated cycloalkanone represented by General Formula (III), comprising: 1: reacting a compound represented by General Formula (I) and an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent; and 2: reacting a crude product obtained in the reacting 1 and a compound represented by General Formula (II) in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by General Formula (III), wherein the reacting 1 and the reacting 2 are consecutively performed, and ##STR00024## wherein: the group -A.sup.1- is an alkylene group having 4 or more and 20 or less of carbon atoms that optionally contains a hetero atom and optionally has a substituent, where the front bond of the group -A.sup.1- refers to a bond that binds to the carbon atom C.sup.1 and the back bond of the group -A.sup.1- refers to a bond that binds to the carbon atom C.sup.2, and R.sup.4 is a hydrogen atom or an alkyl group having 1 or more and 4 or less of carbon atoms.

2-14. (canceled)

15: The method according to claim 1, wherein the group -A.sup.1- is an alkylene group having 10 or more and 14 or less of carbon atoms that optionally has a substituent.

16: The method according to claim 1, wherein the group -A.sup.1- is an alkylene group having 10 or more and 12 or less of carbon atoms.

17: The method according to claim 1, wherein the method in which the reacting 1 and the reacting 2 are consecutively performed comprises no isolation-purification step performed in the course of the method.

18: The method according to claim 1, wherein the first acid catalyst and the second acid catalyst are independently one or more selected from the group consisting of organic sulfonic acids and salts thereof, and inorganic acid salts of pyridine.

19: The method according to claim 18, wherein the organic sulfonic acids are aromatic sulfonic acids.

20: The method according to claim 18, wherein the first acid catalyst and the second acid catalyst are independently selected from the group consisting of compounds represented by Formula (X) below and compounds represented by Formula (XI) below: ##STR00025## where R.sup.21 and R.sup.22 are independently a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms, and X.sup.+ is represented by Formula (XII) or Formula (XIII), and where R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are the same or different and each of them is a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms.

21: The method according to claim 1, wherein the first acid catalyst and the second acid catalyst independently comprises p-toluenesulfonic acid or pyridinium p-toluenesulfonate.

22: The method according to claim 18, wherein the salts of the organic sulfonic acids are pyridinium salts.

23: The method according to claim 18, wherein an acid included in the inorganic acid salts of pyridine is one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfurous acid, nitrous acid, hydrobromic acid, hydroiodic acid, acetic acid, and butyric acid.

24: The method according to claim 1, wherein the first acid catalyst and the second acid catalyst are the same.

25: The method according to claim 1, wherein an amount of the first acid catalyst that is used is 10.sup.−5 equivalents or more and 1 equivalent or less relative to a total amount of the compound of General Formula (I) and the compound of General Formula (II).

26: The method according to claim 1, wherein the reacting 1 is performed at a temperature of 120° C. or higher and 150° C. or lower.

27: The method according to claim 1, wherein the reacting 2 is performed at a temperature of 120° C. or higher and 150° C. or lower.

28: The method according to claim 1, wherein the reacting 1 and the reacting 2 are performed using a rectification column.

29: The method according to claim 1, wherein the reacting 1 and the reacting 2 are performed in one pot.

30: The method according to claim 1, wherein the Formula (I) is Formula (I-1) below, and the Formula (III) is Formula (III-1) below: ##STR00026##

31: A method for synthesizing muscenone in which the α-allylated cycloalkanone of Formula (III-1) produced using the method according to claim 30 is used.

32: A method for synthesizing muscenone, the method comprising: 1: reacting a compound represented by General Formula (I-1) and an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent; 2: reacting a crude product obtained in the reacting 1 and β-methallyl alcohol in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by General Formula (III-1), (i) cyclization of the α-allylated cycloalkanone represented by General Formula (III-1); (ii) hydrogenation; (iii) oxidative cleavage; (iv) reduction; and (v) ring-opening, ##STR00027## wherein the reacting 1 and the reacting 2 are consecutively performed.

33: The method according to claim 32, wherein the method in which the reacting 1 and the reacting 2 are consecutively performed comprises no isolation-purification step performed in the course of the method.

34: The method according to claim 32, wherein the first acid catalyst and the second acid catalyst are independently one or more selected from the group consisting of organic sulfonic acids and salts thereof, and inorganic acid salts of pyridine.

35: The method according to claim 34, wherein the organic sulfonic acids are aromatic sulfonic acids.

Description

EXAMPLES

[0112] Gas Chromatography (GC) Apparatus and Analysis Conditions

[0113] GC apparatus: Model: GC-6850, manufactured by Agilent Technologies

[0114] Column: DB-1 (with an inner diameter of 0.25 mm, a length of 30 m, and a membrane thickness of 0.25 μm), manufactured by J&W

[0115] Carrier gas: He, 1.5 mL/min

[0116] Injection conditions: 300° C., split ratio of 100/1

[0117] Injection amount: 1 μL

[0118] Detection conditions: FID method, 300° C.

[0119] Column temperature conditions: 80° C..fwdarw.rising the temperature at 10° C./minute.fwdarw.keeping the temperature at 300° C. for 10 minutes

[0120] Compound Identification

[0121] Compounds obtained in examples, experimental examples, and the like below were identified using GC (gas chromatography).

[0122] The yield (%) was calculated using the following expression.

[00001]$\begin{array}{cc}\mathrm{Yield}=\frac{\frac{(\begin{array}{c}\begin{array}{c}\begin{array}{c}\mathrm{Weight}\mathrm{of}\mathrm{reaction}\\ \mathrm{end}\mathrm{solution}\mathrm{of}\end{array}\\ \begin{array}{c}2\text{-}\left(2\text{-}\mathrm{methylallyl}\right)\\ \mathrm{cyclododecanone}\end{array}\end{array}\times \\ \mathrm{GC}\mathrm{area}\%\end{array})}{236.4}}{\frac{\begin{array}{c}\mathrm{Feed}\mathrm{amount}\mathrm{of}\mathrm{raw}\\ \mathrm{material}\left(\mathrm{cyclododecanone}\right)\end{array}}{182}}\times 100& \left[\mathrm{Mathematical}\mathrm{Formula}1\right]\end{array}$

[0123] Here, a GC area % refers to a ratio of an output chart area of the component detected using GC to the entire area.

Example 1: Synthesis of 2-(2-methylallyl)cyclododecanone

[0124] ##STR00018##

[0125] (i) Step 1

[0126] Cyclododecanone (I-1) (500.0 g, 2.743 mol), trimethyl orthoformate (349.5 g, 3.292 mol), and methanol (264.3 g, 8.229 mol) were placed into a 2-L four-neck flask and stirred at room temperature into a homogeneous solution. Pyridinium p-toluenesulfonate (PPTS, 0.7 g, 2.743 mmol) was added thereto, stirred, and dissolved. A thermometer, a mechanical stirrer, and a 10-step Sulzer rectification column (manufactured by Kyowa Chemical) were installed on the 2-L four-neck flask. Under a nitrogen atmosphere, stirring of the content in the 2-L four-neck flask was started at an outside temperature of 80° C. A reactant was sampled from the 2-L four-neck flask over time and subjected to GC analysis, and thus the conversion rate of the compound of (I-1) was observed. The reaction was stopped 6 hours after the start of the reaction, and the reaction mixture was cooled.

[0127] Next, methanol and trimethyl orthoformate contained in the product were distilled off under reduced pressure. A K-shaped pipe, a cooling pipe, and a distillate receiver were installed on the 2-L four-neck flask. Under a nitrogen atmosphere, distillation of the product under reduced pressure was started at an outside temperature of 110° C. The pressure was reduced from the ordinary pressure to 66.5 kPa one hour after the start of the distillation, and then the distillation under reduced pressure was continued. The flow of distillate into the receiver stopped in 2 hours, and the distillation under reduced pressure was finished. As a result of gas chromatography analysis on the reaction solution after the distillation, the component composition was as follows: 1,1-dimetoxycyclododecane (XX-1) corresponded to 43.5 GC area %, and 1-methoxy-1-cyclododecene (XXI-1) corresponded to 54.5 GC area %.

##STR00019##

[0128] (ii) Step 2

[0129] A thermometer, a mechanical stirrer, and a 10-step Sulzer rectification column were installed on the 2-L four-neck flask containing the reactants. At room temperature, 6-methallyl alcohol (II-1) (296.7 g, 4.115 mol) was added to the four-neck flask. The content (containing pyridinium p-toluenesulfonate (PPTS, 0.7 g, 2.743 mmol)) in the flask was stirred into a homogeneous system, and then was heated in an oil bath at an outside temperature of 140° C. under nitrogen stream. The top temperature was monitored over time and was confirmed to be 65° C. After 3.5 hours, it was confirmed that the content in the flask became free of 1,1-dimetoxycyclododecane (XX-1) and 1-methoxy-1-cyclododecene (XXI-1), and then the reaction was stopped.

[0130] Next, a K-shaped pipe, a cooling pipe, and a distillate receiver were installed on the 2-L four-neck flask containing the reaction solution (containing 2-(2-methylallyl)cyclododecanone (III-1)), the reaction solution was heated and stirred at 18.0 kPa and 120° C. to distill off 6-methallyl alcohol (II-1) (distilled-off amount: 67.1 g). After the reaction solution was heated and stirred for 2 hours, the pressure was reduced to 16 kPa, and the reaction solution was heated and stirred for another 1 hour in order to complete the distillation.

[0131] After 8-methallyl alcohol (II-1) had been distilled off, the residue was transferred to a 2-L separable reaction container with a jacket, and then alkali water obtained by dissolving K.sub.2HPO.sub.4 (0.4 g, 2.057 mmol) in 20.2 g of ion-exchange water was added thereto. A mechanical stirrer, a thermometer, a Dimroth condenser, and a nitrogen-flow device were installed on the separable reaction container. The mixture in the separable reaction container was stirred at room temperature for 1 hour. After the stirring had been finished, the mixture was heated to 80° C. using a condenser and was then left to stand till layers were separated. An aqueous layer (15.4 g) was removed from the separable reaction container, and then the pH of the residue was checked. The pH was 8.0 (pH test paper).

[0132] Simple distillation was performed in order to distill off the residual B-methallyl alcohol (II-1) and water from the residue. AK-shaped pipe, a cooling pipe, and a distillate receiver were installed on the separable reaction container containing the residue, the residue was heated and stirred at 0.3 kPa and 130° C. for 2 hours to distill off B-methallyl alcohol (II-1) and water. Thus, a residue (671.2 g) was obtained. Gas chromatography analysis on the residue revealed that 2-(2-methylallyl)cyclododecanone (Ill-1) corresponded to 94.7 GC area %. The yield of 2-(2-methylallyl)cyclododecanone (III-1) calculated from the amount of 2-(2-methylallyl)cyclododecanone obtained was 98.1%.

Example 2: Synthesis of 2-(2-methylallyl)cyclododecanone

[0133] ##STR00020##

[0134] (i) Step 1

[0135] After cyclododecanone (I-1) (500.0 g, 2.743 mol), trimethyl orthoformate (349.3 g, 3.292 mol), and methanol (263.7 g, 8.229 mol) were placed into a 2-L four-neck flask, and the air was purged with nitrogen, the resultant mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere into a homogeneous solution. Pyridinium p-toluenesulfonate (PPTS, 0.7 g, 2.743 mmol) was added thereto, stirred, and dissolved. A Dimroth condenser was attached to the 2-L four-neck flask, and a circulator was used to flow warm water at 37° C. in the Dimroth condenser. A Dean-Stark dewatering pipe was attached to an end of the Dimroth condenser, and a 200-mL distillate receiver was attached to the lower portion of the dewatering pipe. The distillate receiver was immersed in ice water and was thus cooled with ice. Another Dimroth condenser was attached to the upper portion of the Dean-Stark dewatering pipe, and another circulator was used to flow cold water at 10° C. in the Dimroth condenser. One end of a silicone tube was attached to the top of the Dimroth condenser cooled to 10° C., and the other end was introduced to an ethanol-dry ice trap. A portion beyond the trap was sealed with nitrogen. Under a nitrogen atmosphere, the content in the 2-L four-neck flask was heated and refluxed at a bath temperature of 80° C. for 8 hours.

[0136] A K-shaped pipe, a cooling pipe, and a distillate receiver were installed on the 2-L four-neck flask containing the reaction end product. Under a nitrogen atmosphere, the solvent was distilled off from the reaction end product at 101.3 kPa over 4.5 hours while the bath temperature was raised from 100° C. to 120° C. As a result of gas chromatography analysis on the reaction solution after the distillation, the component composition was as follows: 1,1-dimetoxycyclododecane (XX-1) corresponded to 25.9 GC area %, 1-methoxy-1-cyclododecene (XXI-1) corresponded to 73.7 GC area %, and cyclododecanone (I-1) corresponded to 0.3 GC area %.

[0137] (ii) Step 2

[0138] A K-shaped pipe, a cooling pipe, and a distillate receiver were installed on the 2-L four-neck flask containing the reactants. B-Methallyl alcohol (II-1) (296.7 g, 4.115 mol) was dripped into the four-neck flask over 8 minutes while the reactants were heated and stirred at a bath temperature of 110° C. under a nitrogen atmosphere. Methanol was distilled off at a bath temperature of 110° C. under nitrogen stream into the four-neck flask till the content of the methallyl cyclododecanone corresponded to 40 to 50 GC area %. After 4 hours, the flow of methanol from the four-neck flask stopped (distilled-off amount: 108.9 g). The K-shaped pipe, the cooling pipe, and the distillate receiver were removed from the four-neck flask, a Dimroth condenser was attached to the four-neck flask, the bath temperature was raised to 130° C., and then the reaction mixture was heated and refluxed for 17 hours.

[0139] Next, a K-shaped pipe, a cooling pipe, and a distillate receiver were installed on the 2-L four-neck flask containing the reaction solution, and the reaction solution was heated and stirred at 18.0 kPa and a bath temperature of 120° C. for 3.5 hours to distill off 8-methallyl alcohol (III-1) (distilled-off amount: 79.7 g). As a result of gas chromatography analysis on the reaction solution after the distillation, the component composition was as follows: 2-(2-methylallyl)cyclododecanone (III-1) corresponded to 92.5 area %.

[0140] Alkali water obtained by dissolving K.sub.2HPO.sub.4 (0.358 g, 2.057 mmol) in 20.0 g of ion-exchange water was added to the 2-L four-neck flask containing the reaction solution after 6-methallyl alcohol (II-1) had been distilled off under reduced pressure, and the resultant mixture was vigorously stirred at room temperature for 1 minute.

[0141] Next, the viscosity of the reaction solution was reduced by raising the bath temperature to 80° C., and then the reaction solution was left to stand for 15 minutes to separate layers. The pH of the aqueous layer of the reaction solution was 8.0 (pH test paper). As a result of gas chromatography analysis on the oil layer of the reaction solution, 2-(2-methylallyl)cyclododecanone (III-1) corresponded to 92.5 area %. The amount of the oil layer obtained was 644.9 g (theoretical amount: 648.5 g). The yield of 2-(2-methylallyl)cyclododecanone (III-1) calculated from the amount of 2(2-methylallyl)cyclododecanone obtained was 92.4%.

Example 3: Synthesis of 2-(2-methylallyl)cyclododecanone

[0142] ##STR00021##

[0143] (i) Step 1

[0144] A mechanical stirrer and a Dimroth condenser were installed on a reaction container with a side arm (manufactured by EYELA, φ30). Cyclododecanone (I-1) (4.4 g, 24.1 mmol), triethyl orthoformate (8.6 g, 58.2 mmol), ethanol (6.6 g, 140.4 mmol), and pyridinium p-toluenesulfonate (0.035 g, 0.13 mmol) were placed thereinto, and were heated and refluxed at a bath temperature of 85° C. for 36 hours while being stirred.

[0145] After the reaction mixture had been cooled, B-methallyl alcohol (II-1) (5.2 g, 72.0 mmol) was added to the reaction mixture. A Dean-Stark trap was installed, the bath temperature was raised to 140° C., and then the reaction mixture was heated and refluxed for 11 hours.

[0146] After the reaction solution had been cooled, a saturated aqueous solution of sodium hydrogen carbonate (10 mL) was added to the reaction solution, and the resultant mixture was stirred for 5 minutes. The oil layer of the obtained reaction end product was diluted with diethyl ether, and then the aqueous layer was removed. The solvent in the oil layer was distilled off under reduced pressure, and thus a reaction end solution was obtained (7.0 g). 2-(2-Methylallyl)cyclododecanone (III-1) in the reaction end solution corresponded to 79.2 GC area %, and the yield was 92.4%.

##STR00022##

[0147] (ii) Step (ii)

[0148] A K-shaped pipe, a cooling pipe, and a distillate receiver were installed on a 300-mL four-neck flask containing the reactants. Under a nitrogen atmosphere, 8-methallyl alcohol (II-1) (29.7 g, 0.411 mol) was dripped into the four-neck flask over 2 minutes while the reactants were heated and stirred at a bath temperature of 110° C. Ethanol was distilled off over 3 hours under nitrogen stream into the four-neck flask (distilled-off amount: 11.54 g). After the flow of ethanol had stopped, the K-shaped pipe, the cooling pipe, and the distillate receiver were removed from the four-neck flask, a Dimroth condenser was attached to the four-neck flask, the bath temperature was raised to 130° C., and then the reaction mixture was heated and refluxed for 4 hours. As a result of gas chromatography analysis on the obtained reaction solution, the component composition was as follows: 2-(2-methylallyl)cyclododecanone (III-1) corresponded to 93.9 area %. It should be noted that the yield of 2-(2-methylallyl)cyclododecanone (III-1) calculated from the GC area % thereof was 99.2%.

[0149] Table 1 below shows the details of all of the examples above.

TABLE-US-00001 TABLE 1 Equivalent of first acid catalyst and Yield of First acid second acid compound catalyst in step 1 catalyst Compound of of Alcohol and second acid relative to raw Formula (II) Formula Raw material in step 1 catalyst in step 2 material.sup.*1 in step 2 (III) (%) Ex. 1 Compound of Methanol PPTS 0.001 Compound of 98.1 Formula (I-1) Formula (II-1) Ex. 2 Compound of Methanol PPTS 0.001 Compound of 92.4 Formula (I-1) Formula (II-1) Ex. 3 Compound of Ethanol PPTS 0.003 Compound of 99.2 Formula (I-1) Formula (II-1) .sup.*1“Raw material” means the compound of General Formula (I).

[0150] As can be appreciated from Table 1 above, with the method of the present invention, it is possible to obtain a highly pure compound of Formula (III) in increased yield from a compound of Formula (I).

[0151] In Examples 4 to 7, the yield of 2-(2-methylallyl)cyclododecanone (III-1) was determined in accordance with the similar procedure. The procedure for Example 4 is described below as a representative procedure, and the addition amounts of reagents are shown in the other examples.

Example 4

[0152] ##STR00023##

[0153] A mechanical stirrer and a Dimroth condenser were installed on a reaction container with a side arm (manufactured by EYELA, φ30). Cyclododecanone (I-1) (4.4 g, 24.1 mmol), trimethyl orthoformate (3.0 g, 28.7 mmol), methanol (2.3 g, 72.4 mmol), and p-toluenesulfonic acid (0.022 g, 0.12 mmol) were placed thereinto, and were heated and refluxed at a bath temperature of 80° C. for 3 hours while being stirred.

[0154] After the reaction mixture had been cooled, 6-methallyl alcohol (II-1) (2.6 g, 36.0 mmol) was added to the reaction mixture. A Dean-Stark trap was installed, the bath temperature was raised to 140° C., and then the reaction mixture was heated and refluxed for 2 hours.

[0155] After the reaction solution had been cooled, a saturated aqueous solution of sodium hydrogen carbonate (10 mL) was added to the reaction solution, and the resultant mixture was stirred for 5 minutes. The oil layer of the obtained reaction end product was diluted with diethyl ether, and then the aqueous layer was removed. The solvent in the oil layer was distilled off under reduced pressure, and thus a reaction end solution was obtained (5.8 g). 2-(2-Methylallyl)cyclododecanone (III-1) in the reaction end solution corresponded to 93.8 GC area %, and the yield was 95.5%.

Example 5

[0156] The procedure was the same as that for Example 4, except that the amounts of the reagents were changed as follows:

[0157] cyclododecanone (I-1) (4.4 g, 24.1 mmol), trimethyl orthoformate (3.0 g, 28.7 mmol), methanol (2.3 g, 72.4 mmol), p-toluenesulfonic acid (0.005 g, 0.027 mmol), and β-methallyl alcohol (II-1) (2.6 g, 36.0 mmol). The weight of the reaction end solution was 5.4 g. 2-(2-Methylallyl)cyclododecanone (III-1) corresponded to 95.8 GC area %, and the yield was 90.9%.

Example 6

[0158] The procedure was the same as that for Example 4, except that the amounts of the reagents were changed as follows:

[0159] cyclododecanone (I-1) (4.4 g, 24.1 mmol), trimethyl orthoformate (3.0 g, 28.7 mmol), methanol (2.3 g, 72.4 mmol), (+)-10-camphorsulfonic acid (0.06 g, 0.25 mmol), and β-methallyl alcohol (II-1) (2.6 g, 36.0 mmol). The weight of the reaction end solution was 5.9 g. 2-(2-Methylallyl)cyclododecanone (III-1) corresponded to 95.3 GC area %, and the yield was 90.9%.

Example 7

[0160] The procedure was the same as that for Example 4, except that the amounts of the reagents were changed as follows:

[0161] cyclododecanone (I-1) (4.4 g, 24.1 mmol), trimethyl orthoformate (3.0 g, 28.7 mmol), methanol (2.3 g, 72.4 mmol), pyridine hydrochloride (0.26 g, 2.5 mmol), and B-methallyl alcohol (II-1) (2.6 g, 36.0 mmol). The weight of the reaction end solution was 5.4 g. 2-(2-Methylallyl)cyclododecanone (III-1) corresponded to 77.1 GC area %, and the yield was 73.7%.

[0162] Tables 2 and 3 below show the details of all of Examples 4 to 7 above and the results obtained therefrom.

TABLE-US-00002 TABLE 2 Yield of First acid Equivalent of compound catalyst in step 1 acid catalysts Compound of of Alcohol and second acid relative to Formula (II) Formula Raw material in step 1 catalyst in step 2 raw material.sup.*1 in step 2 (III) (%) Ex. 4 Compound of Methanol PTS 0.005 Compound of 95.5 Formula (I-1) Formula (II-1) Ex. 5 Compound of Methanol PTS 0.001 Compound of 90.9 Formula (I-1) Formula (II-1) .sup.*1“Raw material” means the compound of General Formula (I).

TABLE-US-00003 TABLE 3 Yield of First acid Equivalent of compound catalyst in step 1 acid catalysts Compound of of Alcohol and second acid relative to Formula (II) Formula Raw material in step 1 catalyst in step 2 raw material.sup.*1 in step 2 (III) (%) Ex. 6 Compound of Methanol (+)-10- 0.01 Compound of 90.9 Formula (I-1) camphorsulfonic Formula (II-1) acid Ex. 7 Compound of Methanol Pyridine 0.1 Compound of 73.7 Formula (I-1) hydrochloride Formula (II-1) .sup.*1“Raw material” means the compound of General Formula (I).

[0163] As can be appreciated from Tables 2 and 3 above, with the method of the present invention, it is possible to obtain a highly pure compound of Formula (III) in increased yield from a compound of Formula (I).

INDUSTRIAL APPLICABILITY

[0164] With the production method of the present invention, it is possible to produce a highly pure compound of Formula (III) in increased yield. Furthermore, the production method of the present invention is useful for a method for producing muscenone.