JP2002020343A - 16-hydroxy-10-oxa-7-hexadecen-1-al and 16-hydroxy-10- oxahexadecan-1-al, method for producing them and method for producing 10-oxahexadecanolide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for producing 10-oxahexadecanolide in good productivity scarcely polluting environments, and to provide important intermediates for producing 10-oxahexadecanolide. SOLUTION: This method for producing the 10-oxahexadecanolide, characterized by hydrogenating 16-hydroxy-10-oxa-7-hexadecen-1-al represented by the general formula (1) in the presence of a catalyst to obtain the 16-hydroxy-10- oxahexadecan-1-al, oxidizing the hydrogenation product and then further subjecting the oxide to a polymerization process and a depolymerization process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound
16-hydroxy-10-oxa-7-hexadecene-1-al, 1
The present invention relates to 6-hydroxy-10-oxahexadecane-1-al and a method for producing them. These novel compounds are useful as intermediates in the production of 10-oxahexadecanolide, a synthetic musk fragrance. The present invention also relates to a novel method for producing 10-oxahexadecanolide.

[0002]

2. Description of the Related Art Synthetic musks having a musk-like aroma are useful as a fragrance material, and many synthetic musks have been produced and actually used. Synthetic musks are classified into macrocyclic musks, nitro musks, polycyclic musks, and other synthetic musks in view of their chemical structure. One of the flavors classified as macrocyclic musks is 10-oxahexadecanolide (Gento Indo , Synthetic perfume (chemical and product knowledge), Chemical Daily, 1996). This fragrance has good aroma characteristics and is used for various compounded fragrances. A method for producing the perfume is also reported in the same book, but during the production process, a chlor reaction of 1,9-nonanediol using an equivalent amount or more of hydrochloric acid, 9- Kurorunonano - comprises oxidation of Le, the processing of the waste produced by these reactions increases the load on the environment, absolutely manufacturing cost due to its processing and the like has become higher. In addition, the reaction efficiency was far from good because, for example, the use of hydrochloric acid or nitric acid in an equivalent amount or more required a large reactor.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing 10-oxahexadecanolide with low environmental load, simple steps and high productivity. It is in. It is also an object of the present invention to provide important production intermediates for the production of 10-oxahexadecanolide.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)

Embedded image 16-hydroxy-10-oxa-7-hexadecene-1 represented by (1)
-R is the following general formula (3)

Embedded image It has been found that 7-oxa-9,14-pentadecadien-1-ol represented by (3) can be easily obtained by hydroformylation in the presence of a catalyst.

Further, by hydrogenating a carbon-carbon double bond of the compound represented by the above formula (1) in the presence of a catalyst, the compound represented by the following general formula (2)

Embedded image The present inventors have found that 16-hydroxy-10-oxahexadecane-1-al represented by the following formula (2) can be obtained, and have completed the present invention.

That is, the present invention provides (1): the following general formula (1)

Embedded image 16-hydroxy-10-oxa-7-hexadecene-1 represented by (1)
-R,

[0007]

Embedded image (2): The following general formula (2) (2) 16-hydroxy-10-oxahexadecane-1-al represented by

(3): The following general formula (3)

Embedded image (3) 16-oxa-9,14-pentadecadien-1-ol represented by the formula
Method for producing hydroxy-10-oxa-7-hexadecene-1-al,

(4): 16 represented by the above general formula (1)
-Hydroxy-10-oxa-7-hexadecene-1-al,
A method for producing 16-hydroxy-10-oxahexadecane-1-al represented by the general formula (2), which comprises hydrogenating in the presence of a catalyst,

(5): The above 16-hydroxy-10-oxa
-7-Hexadecene-1-al is hydrogenated in the presence of a catalyst to obtain 16-hydroxy-10-oxahexadecane-1-al represented by the general formula (2). It is characterized by oxidizing 1-al to obtain 16-hydroxy-10-oxahexadecanoic acid, and then polymerizing and depolymerizing 16-hydroxy-10-oxahexadecanoic acid.
A method for producing 10-oxahexadecanolide.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the novel compound of the present invention will be described. The novel compound 16-hydroxy-10-oxa-7-hexadecene-1-al according to the present invention has the following general formula (1)

Embedded image (1) is represented by

In preparing this compound, the following general formula (11)

Embedded image 15-Hydroxy-9-oxa-2-methyl-6-pentadecene-1-al represented by (11) is often by-produced, but this compound is also novel.

From the above, according to the present invention, the general formula (1)
It can be said that the compound represented by the general formula (1) may include a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (11). The compound represented by the general formula (1) or (11) is
It is a mixture of the cis-form and the trans-form, but may contain a large amount of the cis-form or the trans-form, or may contain only the cis-form or the trans-form.

Further, the following general formula (2)

Embedded image 16-hydroxy-10-oxahexadecane-1-al represented by (2) is also a novel compound referred to in the present invention.

When this compound is prepared, the following general formula (21)

Embedded image In many cases, 15-hydroxy-9-oxa-2-methylpentadecane-1-al represented by the following formula (21) is by-produced, but this compound is also novel.

From the above, according to the present invention, the general formula (2)
It can be said that the compound represented by the general formula (2) may include a mixture of the compound represented by the general formula (2) and the compound represented by the general formula (21).

Hereinafter, a method for producing the novel compound of the present invention will be described. 16-hydroxy-10-oxa-7-hexadecene-1
7-oxa-9,14-pentadecadiene-1 is prepared using a commonly used rhodium or cobalt catalyst.
-All (3) can be easily synthesized by hydroformylation of the terminal carbon-carbon double bond under the pressure of hydrogen and carbon monoxide. At this time, 15-hydroxy-9-oxa-2-methyl-6-pentadecene-1-al (11) is often by-produced as a small component.

The 16-hydroxy-10-oxa-7-hexadecene-1-al (1) of the present invention is synthesized by a hydroformylation reaction of 7-oxa-9,14-pentadecadien-1-ol (3). The hydroformylation reaction catalyst used for this purpose is not particularly limited as long as it is a commonly used catalyst, but among them, a rhodium catalyst is preferable. RhH (CO) (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Rh
Rhodium complexes such as (acac) (CO) ₂ , [Rh (COD) Cl] ₂ , Rh ₄ (CO) ₁₆ (PPh ₃ is triphenylphosphine, acac is acetyl acetate, COD is cyclooctadiene (Shown) and 1 to 100 equivalents of a phosphorus ligand with respect to 1 equivalent of the rhodium complex. The phosphorus ligand has an alkyl group which may have a substituent or an allyl group which may have a substituent (the substituent includes an alkyl group, a halogen atom, an amino group, a sulfo group, and the like). Monodentate or bidentate phosphines or phosphites are preferred.

In the hydroformylation reaction, the amount of the rhodium catalyst used is about 0.00001 to 0.1 mol%, preferably 0.0005 mol, based on 7-oxa-9,14-pentadecadien-1-ol (3). About 0.01 mol%.
Further, the above reaction is carried out usually at a temperature of about room temperature to about 120 ° C, preferably at a temperature of about 40 to 120 ° C, usually for about 1 hour to 64 ° C.
The reaction is completed in about an hour, preferably about 2 hours to about 55 hours, but these conditions can be appropriately changed depending on the amount of the reactant used, the amount of the rhodium catalyst and the like. Further, the above reaction can be carried out without a solvent, but also in a solvent inert to the reaction, such as toluene or tetrahydrofuran. It is also possible to carry out the reaction in a two-layer system of water and a solvent.

This reaction usually proceeds under a mixed gas pressure of hydrogen and carbon monoxide. The ratio of hydrogen to carbon monoxide used is between 1: 1 and 3: 1 (volume ratio). The pressure of the mixed gas used is between 0.2 and 9 MPa, preferably between 0.5 and 5 MPa
It is.

The thus obtained 16-hydroxy-10
-Oxa-7-hexadecene-1-al (1) includes 15-hydroxy-9-oxa-2-methyl-6-pentadecene-1-al (1
1) may be included. The ratio of (1) to (11) is usually 60:40 to 99: 1 (weight ratio).

Starting from the above 16-hydroxy-10-oxa-7-hexadecene-1-al (1), 16-hydroxy-1
Prepare 0-oxahexadecane-1-al (2). That is, by hydrogenating 16-hydroxy-10-oxa-7-hexadecene-1-al (1) in the presence of a hydrogenation catalyst in a hydrogen atmosphere, 16-hydroxy-10-oxahexadecane-1-al ( 2) can be synthesized. At this time, 15-hydroxy-9-oxa-2-methylpentadecane-1-al (21) is by-produced. The main reason is 16-hydroxy-
This is because 15-hydroxy-9-oxa-2-methyl-6-pentadecene-1-al (11) is mixed in 10-oxa-7-hexadecene-1-al (1).

Hereinafter, the reaction conditions for the hydrogenation will be described. The hydrogenation catalyst used in the hydrogenation reaction of 16-hydroxy-10-oxa-7-hexadecene-1-al (1) is not particularly limited as long as it is a commonly used catalyst. A catalyst is suitable. Examples of the palladium catalyst include hydrogenation catalysts such as palladium alumina, palladium carbon, and palladium-barium sulfate.

The amount of the hydrogenation catalyst is 16-hydroxy-10
0.0-oxa-7-hexadecene-1-al (1)
About 01 to 1% by weight, preferably 0.005 to 0.1% by weight
%. Further, the above reaction can be carried out without a solvent, but also in a solvent inert to the reaction, such as toluene or tetrahydrofuran. Furthermore, the hydrogenation reaction
The temperature is usually from room temperature to about 100 ° C., preferably 40 to 80 ° C.
The reaction is usually carried out at a temperature of about 1 ° C for about 1 hour to 30 hours, preferably for about 5 hours to 20 hours. sell.

This reaction is usually carried out under hydrogen pressure. The pressure of the hydrogen used is between 0.1 and 5 MPa, preferably
0.5 to 3 MPa. The thus obtained 16-hydroxy-10-oxa-7-hexadecane-1-al (2) has
15-hydroxy-9-oxa-2-methyl-6-pentadecane-1-
An arc (21) may be included. The ratio between (2) and (21) is usually 60:40 to 99: 1 (weight ratio).

The 16-hydroxy-10-oxahexadecane-1-al (2) thus obtained is oxidized in the presence of, for example, aqueous hydrogen peroxide or air to obtain 16-hydroxy-10-oxahexadecanoic acid (4). Can be easily synthesized. At this time, 15-hydroxy-9-oxa-2-
Methylpentadecanoic acid (41) is often produced as a by-product.

Hereinafter, the oxidation reaction conditions will be described. 16
The method used to synthesize 16-hydroxy-10-oxa-7-hexadecanoic acid (4) from 1-hydroxy-10-oxa-7-hexadecane-1-al (2) is based on an aldehyde oxidation reaction. is there. The oxidation reaction of aldehyde is, for example,
It is carried out by a method of performing an oxidation reaction in the presence of 5 to 35% aqueous hydrogen peroxide or a method of using air in the presence of a catalyst.

In the oxidation reaction using aqueous hydrogen peroxide,
The amount of 5 to 35% aqueous hydrogen peroxide used is about 1 to 1.4 equivalents of hydrogen peroxide per 1 equivalent of 16-hydroxy-10-oxa-7-hexadecane-1-al (2). And preferably about 1.05 to 1.2 equivalents. Further, the reaction is usually carried out at a temperature of about 100 ° C. or lower, preferably about 5 to 80 ° C., usually for about 1 hour to 30 hours, preferably
The reaction is completed in about 3 to 20 hours.

In the oxidation reaction using air, examples of the oxidation reaction catalyst used include metal halides such as iron, nickel, cobalt, ruthenium, and copper.

In the air oxidation reaction, the amount of the catalyst used is about 0.001 to 0.1 mol% based on 16-hydroxy-10-oxa-7-hexadecane-1-al (2),
Preferably, it is about 0.002 to 0.01 mol%. Further, the reaction is completed at a temperature of usually about 0 ° C. to 100 ° C., preferably about 20 ° C. to 60 ° C., usually for about 1 hour to 20 hours, preferably for about 5 hours to 10 hours. However, these conditions can be appropriately changed depending on the amount of the reactants used, the amount of the air oxidation catalyst, and the like. This reaction is usually allowed to proceed by blowing air without solvent or in the presence of various commonly used polar or non-polar solvents.

The 16-hydroxy-10 thus obtained
-Oxa-7-hexadecanoic acid (4) has 15-hydroxy-9-
Oxa-2-methyl-6-pentadecanoic acid (41) may be included. The ratio between (4) and (41) is usually 60: 4
0 to 99: 1 (weight ratio).

16-hydroxy-10 obtained by the above method
-Oxahexadecanoic acid (4) is useful as an intermediate for producing 10-oxahexadecanolide (5). That is, 10-oxahexadecanolide (5) can be easily prepared by polymerizing 16-hydroxy-10-oxahexadecanoic acid (4) in the presence or absence of a catalyst, and then performing depolymerization in the presence of a catalyst. Can be synthesized. In this case, 2-methyl-9-
Oxapentadecanolide (51) is often produced as a by-product. This is because, in many cases, 15-hydroxy-9-oxa-2-methylpentadecanoic acid (41) is mixed with 16-hydroxy-10-oxahexadecanoic acid (4) as a starting material.

The polymerization reaction is carried out without a catalyst or using a catalyst. The catalyst for the polymerization reaction is not particularly limited as long as it is a commonly used catalyst such as an inorganic salt or an organic metal. In the polymerization reaction, the amount of the catalyst used is about 0.1 to 5% by weight, preferably about 1 to 3% by weight, based on 1 equivalent of 16-hydroxy-10-oxa-7-hexadecanoic acid (4). is there.

The polymerization reaction is carried out at a temperature of about 150 to 200 ° C., usually for about 1 to 5 hours under a reduced pressure of 10 to 1300 Pa.

Subsequently, a depolymerization reaction is performed. In the depolymerization reaction, the catalyst to be used is not particularly limited as long as it is a commonly used catalyst such as an inorganic salt or an organic metal. In the depolymerization reaction, the amount of the catalyst used is
Poly (16-hydroxy-10-oxa-7-hexadecanoic acid) obtained by the polymerization reaction, or poly (16-hydroxy-10-oxa-7-hexadecanoic acid) and poly (15-hydroxy-9-oxa-2) -Methyl-6-pentadecanoic acid) with respect to the total amount of about 0.1 to 5% by weight, preferably 1 to 5% by weight.
About 3% by weight. Further, the reaction is usually performed at 210 to 310.
The reaction is completed at a temperature of about ° C., usually for about 5 to 40 hours, but these conditions can be appropriately changed depending on the amount of the reactants used.

The 10-oxahexadecanolide (5) thus obtained may contain 2-methyl-9-oxapentadecanolide (51) as a by-product. In that case, the ratio of (5) to (51) is usually 60:40 to 99: 1
(Weight ratio).

7-oxa-9,14-pentadecadien-1-ol (3), which is a starting material for preparing the novel compound (1) of the present invention, is shown in UK Patent Application GB 2114974A. It can be synthesized according to the method. That is, it can be easily synthesized by reacting 1,6-hexanediol (6) with butadiene (7) in the presence of a palladium catalyst.

The reaction conditions will be described in more detail.
You. 1,6-hexanediol (6) and butadiene (7)
Of 7-oxa-9,14-pentadecadie by telomerization
Used for synthesizing 1-ol (3)
PdCl_Two, Pd (CH_ThreeCOO)_Two, Pd (acetylace
tonato)_Two, PdCl_Two(CH _ThreeCN)_Two, Pd_Two(dibenezylideneaceton
e)_Three, Pd (PPh_Three)_FourZero-valent or divalent palladium complex
1 to 6 equivalents of phosphine to 1 equivalent of palladium complex
And a catalyst formed with a ligand. Phosph above
Examples of the quinone ligand include an alkyl group which may have a substituent.
Or a monodentate or di-substituted aryl group which may have a substituent.
Locus phosphines are preferred. As a substituent here
Is an alkyl group, halogen atom, amino group, sulfo group, etc.
Is mentioned.

In the telomerization reaction, butadiene (7) is added to 1 equivalent of 1,6-hexanediol (6)
It is usually 2 to 5 equivalents, preferably 2 to 3 equivalents. In the telomerization reaction, the amount of the palladium catalyst used is 0.001 to 1 with respect to 1,6-hexanediol (6).
mol%, preferably about 0.002 to 0.01 mol%.

Further, the reaction is carried out usually at a temperature of about 50 to 100 ° C., preferably about 70 to 90 ° C., usually for about 1 to 64 hours, preferably for about 5 to 24 hours. However, these conditions can be appropriately changed depending on the amounts of the reactants used, the amount of the palladium catalyst, and the like. This reaction usually proceeds in an atmosphere of an inert gas such as nitrogen gas or argon gas. The purity of the 7-oxa-9,14-pentadecadien-1-ol (3) thus obtained is 90% or more.

[0041]

The present invention will be described below in detail with reference to comparative examples and examples, but the present invention is not limited to these examples, and may be changed without departing from the scope of the present invention. Good. ¹ H-NMR spectrum: DRX-500 type apparatus (manufactured by Bruker) Internal standard substance: tetramethylsilane ¹³ C-NMR spectrum: DRX-500 type apparatus (manufactured by Bruker) Internal standard substance: chloroform Gas chromatograph apparatus: GC 353 (GL Sci
columns): TC-1 (30mx 0.25mm) (G
L Sciences) GC-MS device: HP-6890MSD (Hewle
tt Packard)

[0042]

Reference Example 1 Synthesis of 7-oxa-9,14-pentadecadien-1-ol (3) 1,18-hexadiol 1418 g (12 mol), triphenylphosphine was placed in a 5 L autoclave under a nitrogen atmosphere. 314.7
mg (1.2 mmol), palladium acetate (134.7 mg, 0.6 mmo
l), 1305 g (24.13 mol) of 1,3-butadiene,
For 18 hours to obtain a pale yellow reaction solution. The reaction solution was purified by distillation to obtain 888.2 g (GC purity 96.1%) of the title compound. Boiling point: 125-131 ° C / 26 Pa

¹ H NMR (500 MHz, CDCl ₃ ): δ 5.80 (ddt,
J = 17.1, 10.3, 6.7 Hz, 1H), 5.68 (dt, J = 15.4, 6.7
Hz, 1H), 5.56 (dt, J = 15.4, 6.2 Hz, 1H), 5.00 (d
d, J = 17.2, 2.1 Hz, 1H), 4.95 (dt, J = 10.2, 2.1 H
z, 1H), 3.90 (d, J = 6.1 Hz, 2H), 3.62 (t, J = 6.6 H
z, 2H), 3.40 (t, J = 6.6 Hz, 2H), 2.06 (m, 4H), 1.
58 (m, 4H), 1.48 (m, 2H), 1.38 (m, 4H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 138.55, 133.97, 126.70,
114.47, 71.46, 69.97, 62.70, 33.13, 32.60, 31.58,
29.62, 28.19, 25.94, 25.54 m / z: 226 (M ⁺ ), 139, 126, 108, 101, 93, 83, 67, 55,
41, 29

[0044]

Example 1 16-hydroxy-10-oxa-7-hexadecene
Synthesis of 1-al (1) 7-oxa-9,14-pentadecadien-1-ol (3) obtained in Reference Example 1 in a 5 L autoclave under a nitrogen atmosphere.
1001 g (4.42 mol), tris (metasulfophenyl) phosphine-sodium salt 1.61 g (4.42 mmol), RhH (CO) (PP
h ₃ ) ₃ 203 mg (0.221 mmol) and 250 mL of H ₂ O were added, and the mixture of carbon monoxide and hydrogen (CO / H ₂ = 1/1) was replaced three times.
5 MPa was charged. After heating to 90 ° C., the mixed gas of carbon monoxide and hydrogen was pressurized to 4 MPa, and at this point, the reaction was started.

Up to 50% conversion at 90 ° C., 4 MPa, conversion
Hydroformylation was carried out at 80 ° C. and 1 MPa up to 70% and thereafter at 70 ° C. and 0.5 MPa for a total of 55 hours. 1 toluene
L was added and centrifuged at 3000 rpm for 5 minutes to separate an aqueous layer and an organic layer. Further, 250 mL of H ₂ O was added, and separation was performed in the same manner. The toluene was concentrated under reduced pressure to give 1113.4 g of the title compound (yield 111.3% by weight, GC purity 79.1%, 16-hydroxy-10-oxa-7-hexadecene-1-al (1) / 15).
-Hydroxy-9-oxa-2-methyl-6-pentadecene-1-
Earl (11) = 68.1 / 31.9).

Compound (1): ¹ H NMR (500 MHz, CDC
l ₃ ): δ 9.77 (t, J = 1.8 Hz, 1H), 5.66 (m, 1H), 5.55
(m, 1H), 3.90 (d, J = 5.6 Hz, 2H), 3.65 (t, J = 6.
5 Hz, 2H), 3.41 (t, J = 6.6 Hz, 2H), 2.43 (dt, J =
1.7, 7.3 Hz, 2H), 2.05 (m, 2H), 1.58 (m, 6H), 1.37
(m, 10H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 202.80, 133.92, 126.6
5, 71.42, 70.01, 62.70, 43.72, 32.58, 31.92, 29.60,
28.66, 28.55, 25.92, 25.52, 21.80 m / z: 256 (M ⁺ ), 138, 101, 83, 67, 55, 41, 29

Compound (11): ¹ H NMR (500 MHz, CDC
l ₃ ): δ9.77 (d, J = 2.0 Hz, 1H), 5.66 (dt, J = 15.4, 6.
6 Hz, 1H), 5.57 (dt, J = 15.4, 6.0 Hz, 1H), 3.90 (d,
J = 6.0 Hz, 2H), 3.63 (t, J = 6.6 Hz, 2H), 3.40 (t, J = 6.
6 Hz, 2H), 2.34 (m, 1H), 2.07 (brq, J = 6.9 Hz, 2H),
1.58 (m, 4H), 1.37 (m, 8H), 1.09 (d, J = 1.2 Hz, 3H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 205.10, 133.37, 127.0
8, 71.37, 70.08, 62.78, 46.12, 32.62, 32.12, 29.9
1, 29.63, 26.29, 25.95, 25.55, 13.25 MS m / z: 256 (M ⁺ ), 138, 101, 83, 67, 55, 41, 29

[0048]

Example 2 16-hydroxy-10-oxahexadecane-1-
Synthesis of Earl (2) 16-hydroxy-1 in a 5 L autoclave under nitrogen atmosphere
565.46 g of hydroformylated product of 0-oxa-7-hexadecene-1-al (1) (GC purity 62.6%, 16-hydroxy-10-oxa-7-hexadecene-1-al (1) / 15-hydroxy-
9-oxa-2-methyl-6-pentadecene-1-al (1
1) Add a solution of 71.5 / 28.5) in toluene (566 mL) and add 5% P
2.83 g of d / Al ₂ O ₃ was added, and the mixture was stirred at a hydrogen pressure of 2 MPa and 40 ° C. for 20 hours. The catalyst was filtered and toluene was distilled off under reduced pressure to give 567.71 g of the title compound (yield 100.4% by weight, GC purity 66.6%, 16-hydroxy-10-oxahexadecane-1-al (2) / 15-hydroxy -9-oxa-2-methylpentadecane-1-al (21) = 72.0 / 28.0) was obtained.

Compound (2): ¹ H NMR (500 MHz, CDC
l ₃ ): δ 9.69 (t, J = 1.8 Hz, 1H), 3.55 (t, J = 6.7 H
z, 2H), 3.34 (t, J = 6.6 Hz, 2H), 3.33 (t, J = 6.7 H
z, 2H), 2.36 (dt, J = 1.9, 5.5 Hz, 2H), 1.58-1.47
(m, 8H), 1.33-1.21 (m, 12H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 202.85, 70.72, 70.64,
62.51, 43.70, 32.52, 29.52, 29.28, 29.11, 29.06, 2
8.91, 25.93, 25.85, 25.46, 21.88 MS m / z: 258 (M ⁺ ), 157, 123, 99, 83, 67, 55, 41, 29

(21): ¹ H NMR (500 MHz, CDCl ₃ ): δ
9.61 (d, J = 2.0 Hz, 1H), 3.63 (t, J = 6.6 Hz, 2H), 3.4
0 (t, J = 6.6 Hz, 2H), 3.39 (t, J = 6.6 Hz, 2H), 2.33
(m, 1H), 1.57 (m, 6H), 1.39-1.31 (m, 12H), 1.09 (d,
J = 6.9 Hz, 3H) ¹³ C NMR (126 MHz, CDCl ₃ ): δ 205.36, 70.74, 70.73,
62.71, 46.20, 32.60, 30.35, 29.60, 29.55, 29.36, 2
6.79, 25.92, 25.92, 25.52, 13.23 MS m / z: 258 (M ⁺ ), 140, 123, 99, 83, 55, 41, 29

[0051]

Reference Example 2 Synthesis of 16-hydroxy-10-oxa-7-hexadecanoic acid (4) Hydrogenation of hydroformylation of 7-oxa-9,14-pentadecadien-1-ol (3) in a 200 mL three-necked flask 9.64 g (37.3 mmol, GC purity 99.4%, (16
-Hydroxy-10-oxahexadecane-1-al (2) / 1
5-hydroxy-9-oxa-2-methylpentadecane-1-al (21) = 83.1 / 16.9), isobutyl alcohol 100 m
_{L, NaH 2 PO 4 · 2H} 2 O 1.17 g (7.5 mmol), H 2 O 20 mL, 35
4.3 mL (44.9 mmol) of H ₂ O ₂ was added, and 5.92 g (52.4 mmol) of NaClO ₂ (purity 80%) dissolved in 50 mL of H ₂ O was added at 10 ° C.
In the following, the solution was dropped over 2 hours. After the dropwise addition, the mixture was stirred at 10 ° C. or lower for 1 hour, and the peroxide was neutralized with NaHSO ₃ . After separating the organic layer and the aqueous layer, the aqueous layer was extracted with ethyl acetate, the combined organic layers were dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 9.3 g of the title compound.

[0052]

Example 3 Synthesis of 10-oxahexadecanolide (5) Compound 33.3 obtained in Reference Example 2 was placed in a 200 mL three-necked flask.
g, polyethylene glycol (# 1540) 3.33 g, Na ₂ CO ₃
999 mg was added, heated to 150 ° C., and stirred at 1300-130 Pa for 1 hour, then raised to 200 ° C., and stirred for 2 hours to polymerize. Thereafter, depolymerization was performed at 250-300 ° C. for 8 hours to give 20.35 g of the title compound (yield 61.1% by weight, GC purity 90.2%).
%, 10-oxahexadecanolide (5) / 2-methyl-9-oxapentadecanolide (51) = 83.8 / 16.2).

[0053]

According to the present invention, a synthetic musk fragrance 10
Intermediate for the preparation of 1-oxahexadecanolide, ie, 16-hydroxy-10-oxa-7-hexadecene-1-al (1), 16
-Hydroxy-10-oxahexadecane-1-al (2) could be provided. These compounds (1) are composed of 7-oxa-9,14
Can be easily prepared from -pentadecadien-1-ol (3), and compound (2) can be easily prepared from compound (1). Furthermore, after oxidizing the compound (2), the oxide was polymerized and depolymerized, whereby 10-oxahexadecanolide could be produced with high productivity by a simple process. This method is also a method with a small burden on the environment, such as a small amount of waste liquid to be treated.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ken Suzuki 1-4-11, Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Takasago International Co., Ltd. (72) Inventor Yoji Hori, Nishi-Hachiman, Hiratsuka-shi, Kanagawa 4-11, Takasago International Co., Ltd. (72) Inventor: Toshimitsu Hagiwara 4-1-1, Nishihachiman, Hiratsuka-shi, Kanagawa Prefecture F-term in the Advanced Research Laboratory, Takasago International Co., Ltd. 4H006 AA01 AA02 AB84 AC11 AC45 AC46 BD70 BE20 BE40 4H039 CA62 CF10

Claims (5)

[Claims] (1) The following general formula (1): 16-hydroxy-10-oxa-7-hexadecene-1 represented by (1)
-R. 2. A compound represented by the following general formula (2): (2) 16-hydroxy-10-oxahexadecane-1-al represented by the following formula: [3] The following general formula (3): (3) hydroformylation of 7-oxa-9,14-pentadecadien-1-ol represented by the following formula, wherein 16-hydroxy-10-oxa-7-hexadecene-1-al: Manufacturing method. 4. A method for producing 16-hydroxy-10-oxahexadecane-1-al, comprising hydrogenating 16-hydroxy-10-oxa-7-hexadecene-1-al in the presence of a catalyst. 5. A method of hydrogenating 16-hydroxy-10-oxa-7-hexadecene-1-al in the presence of a catalyst to give 16-hydroxy-10-oxa-7-hexadecene-1-al.
-10-oxahexadecane-1-al is obtained, and the 16-hydroxy-10-oxahexadecane-1-al is oxidized to give 16-oxahexadecane-1-al.
Hydroxy-10-oxahexadecanoic acid was obtained, followed by 16-
A method for producing 10-oxahexadecanolide, comprising polymerizing and depolymerizing hydroxy-10-oxahexadecanoic acid.