JPS6054377A - Method for producing 8β,12-epoxy-13,14,15,16,17-pentanollabdane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention processes a compound represented by the following general formula ([) to produce 8β,12-epoxy-13,14,15,16, The present invention relates to a method for producing 17-pentanollabdan. According to the nomenclature of Chemical Abstracts, compound formula (b) is dodecahyde 0-6
．． 6.9a-trimethylnaphtho[2,1b)furan.

Compound (b) is useful as a fragrance having an excellent amber aroma.

A compound called ambrox, which has an amber scent, is manufactured using manur and scleraol as raw materials, but these are both compounds obtained by extracting from coniferous trees produced in New Sealant, and their production is small. It's expensive.

The purpose of the present invention is to provide a method for producing c4t, a compound with an amber scent, from biopsied tar that can be produced in large quantities and is inexpensive.
) (including compound (ISL) and (Ib)), which is independent of biopsy resin.

Biopsy resin contains various compounds, the main component of which is l/bopimaric acid (compound (Ia) below). The match ranges from about 15% to over 50%, such as Eva, OrganikΦ
Synthesis (Organic Synthesis,
Co11active Volume V, 69
It can be easily purified by the method described on page 9). Compound (Ia
) is reacted with diazomethane to obtain methyl levopimarate (compound (Ib) below). Compound (It))
Upon oxidation, compound (Ila) is obtained. As the oxidation method, for example, a combination of ozone oxidation and Jones oxidation is used. In this case, for ozone oxidation, ethyl acetate or a methylene chloride-methyl alcohol mixture is used as a solvent, and ocinide is generated with ozone-containing gas at 5°C or less, especially -70"C, and the ocinide is converted into potassium iodide or It is decomposed by dimethyl sulfide.The above compound (■a) is contained in the product of this ozone oxidation, but by further Jones oxidation of the product, that is, the product is decomposed by a7ton Km. The yield of compound (Ila) can be increased by adding Jones reagent (chromic acid-sulfuric acid aqueous solution) and reacting at -10°C to 20°C. From the Jones oxidized product, compound (Ila) can be converted to a saponified product. The compound (Ib) can be easily purified by silica gel column chromatography by reacting it with diazomethane and converting it into compound (Ib). When reacted in tetrahydrofuran, ethyl ether, etc. for about 0 to 60'0, for about 0.5 to 12 hours, the compound (to) is obtained.

When the compound (Pla) is dissolved in a basic solvent such as pyridine and reacted with methanesulfonyl chloride, the compound (Pla
) is obtained, and the reaction temperature at this time is preferably 0 to 50°C, and the reaction time is preferably 6 to 48 hours.

Further, when compound (2) is reacted with Pi) luenesulfonyl chloride under the same conditions as above, compound (PIb) is obtained.

When compound (IVa) or (*b) is treated with a reducing agent, compound (b) is obtained. As the reducing agent, for example, sodium iodide-zinc powder is used, and in this case, the reaction is carried out at 80 to 140°C for 1 to 12 hours in N,N-dimethylformamide, hexamethyldriamide phosphate, etc. is appropriate.

There is also the following alternative method for obtaining compound (b) from compound (lVa) or (PIb). That is, when these are hydrolyzed under acidic conditions or basic conditions, compound CWC> is obtained, and when this is oxidized using an oxidizing agent, compound (IVd) is obtained, but as the oxidizing agent at this time, For example, using pyridinium chlorochromate or chromic acid-pyridine complex, 0 to 30°C, 0.5
Allow to react for ~5 hours.

Compound (Wd) is subjected to Wolff-Kissiner reduction to obtain compound (b). That is, when the aldehyde group of compound (lId) is changed to human dicine or semicarbazone and heated in the presence of a strong base such as an alkali metal alkoxide, compound (b) is obtained.

The compound (lVe) can also be reduced by desulfurization using a reducing agent such as Raney nickel.
can be obtained.

There is also the following alternative method for obtaining compound (IvC), (lVa'), or (vb) from compound (Ilb). That is, when compound (Ib) is reduced using sodium borohydride under basic conditions, compound (a) is obtained. When this is reduced using diborane, compound (II/f) is obtained. Compound (Wf
) is reduced using lithium aluminum hydride,
A compound (Pie) is obtained. When this product is dissolved in a basic solvent such as pyridine and reacted with methanesulfonyl chloride, compound (Wa) is obtained.Similarly, when compound (IVc) is reacted with P-toluenesulfonyl chloride, compound (% lb) is obtained.

Compound (lVe) can also be obtained by dissolving compound (nb) in a solvent such as toluene or benzene, adding dimethyl sulfoxide and chlorotrimethylsilane, and reacting at 15 to 110°C for 10 minutes to 24 hours.

The thus obtained compound (lVe) or the same (lVa
) or (lVb) can be led to compound (b) by the method described above.

Here, compound (1), compound (1k), compound Nb); compound (II), compound (■a), compound (nb); compound (to); compound axis, compound (lva), compound (tvb) , Same (We)
, the same (fVd), the same (IVe), the same (+Vt); the compound (to); the chemical formula of the compound (b) are collectively shown. However, R1 is CO, II or co,! cn, group, R
8 is CHOlCOilH CHs080. C6H, C1
1. Indicates one group selected from the groups.

I When R1 is CO-■ Compound (Ia), R1 is C0Bc
When H1O, compound (Ib) I When R1 is GO, CH and R2 is CO□H, compound (1
1a); Rt KaC05CH* % R, KaCO
, CH, (F)+4J, compound (fib) 3 to compound ω If R8 is CH,080,CH8, compound (Wa)
; When Rs is C11,080, C, ll4ell, the compound (lVb); R,.

In this case, the compound (iVe); If It is Co, CH, +7), the compound (lVf) Compound (b) Examples of the present invention will be described next, but the present invention is not limited thereto.

Example (1) Preparation of compound (nb) from compound (Ib) Methyl levopimarate (compound (lb) zsf was dissolved in 20 ml of methylene chloride, and 10 g/ml of methyl alcohol was added. This solution was diluted with dry ice-acetone cryogen. -70℃
Ozone-oxygen mixed gas was blown in for 1 hour while cooling to . Next, nitrogen gas was blown in to remove excess ozone, and then 2.5 ml of dimethyl sulfide was added and the temperature was returned to room temperature.

After concentrating the reaction solution under reduced pressure, it was dissolved in 50 ml of acetone.
Under water cooling, use Jones reagent (chromic acid 13.31 to sulfuric acid 11
5g/2×tl-dissolved in 25g/water) was added dropwise, and after the dropwise addition, the mixture was stirred for 1 hour under water cooling. Add 2 ml of isopropyl alcohol to decompose excess oxidizing agent, add 2 ml of water,
00- and 200 ml of ethyl ether were added to perform ether extraction. Add 2N potassium hydroxide aqueous solution 2 to the ether layer.
00 liter was added and the saponified product was extracted into the aqueous layer. The aqueous layer from which the saponified products were extracted was made acidic by adding hydrochloric acid, ethyl ether was added, and the saponified products were extracted into the ether layer. This ether layer was washed with a saturated aqueous solution of IJ and dehydrated with anhydrous sodium sulfate, and then an ethyl ether solution of diazomethane was added to convert the carboxylic acid into a methyl ester. The reaction solution was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography (hexane:ethyl acetate 5:1) using silica gel to obtain compound (Ub) 1.21.

Compound 'Ill (llb): Pale yellow oil C17H
,05 (molecular weight 310) yield 48.9chi (counter compound (I)
b)), IR: 1730 cm-';1"C-N
MR: 209.6 ppm (C-81,:C=0)
, 178.4 I) Ilm (C-18, -COO-)
, 173.4 ppm (C-12, -COO-),
52.1 ppm (-OCI(B), 51.7
ppm (-0CHa) (2) Compound (nb) - Compound (IVa) In a nitrogen gas atmosphere, 200 m of 2.711 lithium aluminum hydride in tetrahydrofuran
compound (Ilb) 7.1 suspension at room temperature. 3 Oystful of tetrahydrofuran solution was added dropwise with stirring, and then refluxed for 1 hour. After cooling, a saturated aqueous sodium sulfate solution was added to remove the white precipitate. The filtrate was filtered under reduced pressure to obtain crude compound 010. Add this to pyridine 2
00 vrl, 5.0 ml of methanesulfonyl chloride was added under water cooling, and then allowed to stand at room temperature for 2 days. Ether extraction was performed by adding 500 g of ether and 500 ml of water to this liquid. The ether layer was washed with dilute hydrochloric acid and saturated aqueous solution, and then dehydrated with anhydrous sodium sulfate. The residue obtained by further concentration under reduced pressure was subjected to silica gel column chromatography (hexane:ethyl acetate 3:1) to obtain compound (■a) 1. By obtained 0 Compound (IVa): pale yellow oil, Cl8HfiO4S
(molecular weight 316), yield 25.2'16 (counter compound (I)
lb)) IR: 1350 all-1, 1175cl
l-', (-0SO2CH,)18CNMR7'1.
'l I)l)m (C-18, -CH, -080, -
'1), 77.3 PPm (C-6, CH-0-)
, 66.2 ppm (C-12, -CH20-)
, 37.0 ppm (-080□CH,) (3) Compound (IVa) - Compound (b) Compound (IVa) 6. Of
Dissolved in 50ml of N,N-dimethylformamide, zinc powder (activated by acid washing)6. Of and sodium iodide Ilf were added, heated to 115°C, and stirred for 6 hours. After cooling, 100 g of ethyl acetate was added and filtered. The filtrate was washed with an aqueous sodium chloride solution and a saturated aqueous sodium chloride solution, and then dehydrated with anhydrous sodium sulfate. The residue obtained by further concentration under reduced pressure was subjected to silica gel chromatography (hexane: ethyl acetate 20:1) to obtain compound (b), i.e. 8β, 12-epoxy-13
, 14,15,16,17-bentanollabdane 2.2
2.4N of compound (IVa) was obtained.

Compound (b): Colorless crystals, melting point 54°C to 55°C Cll1
H260 (molecular weight 222) yield 52.2% (counter compound (
fVa)), IR: 1040 cm-'I8(JJM
R77.8ppm (C-s, :CHO), 66.4
ppm (C-12, -cli, o-), 33.8
ppm (C-18, -C horse), 22.2 ppm (C
-19, -CI(a), 15.5 ppm (C-2
0, -CH,) Procedural amendment 1 Indication of case Patent application 1982-/Otsu tl 7f1 No. p Title of invention 8β, 12-epoxy-13, 14, 15,
16,17-Production method of pentanollabdane 3 Relationship with the case of the person making the amendment Patent applicant address (residence) 671-4 Mizuashi, Noro-cho, Kakogawa-shi, Hyogo Prefecture Name and title) Harima Kasei Kogyo Co., Ltd. μ, representative The applicant and one other person (date: Showa year, month, day) are subject to spontaneous amendment. Application, title of invention column, specification, and detailed description of invention column.

■ The field for the title of the invention in the application will be amended to read "Process for producing 8β,12-epoxy-13,14,15,16,17-pentanollabdane."

■ In the 3rd picture, line 8 of the specification, the phrase "as a fragrance" should be corrected to "as a fragrance."

7, Taji=Kotsuke: 2;: 2, j, (shiσ)) Ko・
6) - 'I) 'TNT J, i')fl''*
'1, A(1)

Claims (1)

[Claims] A compound represented by the following general formula (1) 't' is treated with an oxidizing agent to obtain a compound represented by the following general formula (n), which is then treated with a reducing agent or a reducing agent and a dehydrating agent. 8β, 12 represented by the following general formula (b), which is treated to form a compound represented by the following general formula (good), which is further treated with a reducing agent, or a reducing agent and an oxidizing agent.
- A method for producing epoxy-13,14,15,16,17-pentanollabdane. (In the formula) R, CO, H%j 7jd -CO, c)
l, ; R, bar CIK), or -CO□H1 or -CO□C) I, ;R, is -CO, II, or -C
O, CH, or diCH20H, or -C1120
80□C11j,・Mafc is 10) I2080. C,
Represents H4CH. )