JPS62209045A - Aminooxyterpene alcohol and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is H, lower alkanoyl or benzyl; R<2> and R<3> are lower alkyl or together form tetramethylene; n is 0 or 1). EXAMPLE:4-(Dimethylaminooxy)-3-methyl-2-buten-1-ol. USE:A synthetic intermediate for oxoterpene alcohols, e.g. 4-acetoxy-2-methyl-2- butenal, etc., useful as a synthetic raw material for vitamin A or derivatives thereof. PREPARATION:An aminoterpene alcohol derivative expressed by formula II is reacted with an organic peracid or hydrogen peroxide to give a product, which is then heat-treated to afford a compound expressed by formula III. The resultant compound expressed by formula III is, as necessary, hydrolyzed to provide the aimed compound expressed by formula I.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a compound of the general formula (where Bl represents a hydrogen atom, a lower alkanoyl group or a benzyl group, and Bl and B3 represent a lower alkyl group or - together) represents a tetramethylene group, and n (
io or an integer of 1) and a method for producing the same.

The aminooxyterpene alcohols represented by the general formula m provided by the present invention are useful as raw materials for the synthesis of vitamin A or its derivatives, which are used as medicines or feed additives. It is useful as a synthetic intermediate for producing oxoterpene alcohols such as butynal, 8-acetoxy-2,6-dimethyl-2,6-octagenal, etc. In Ingrid: x-(Angewandte
Ohemie International Edit
ion in English) @ Volume 16 (19
77), pp. 423-429; Chemistry Letters 198
5, pp. 1883-1886, etc.].

[Conventional technology]

Conventionally, among the oxoterpene alcohols, 4-7cetoxy-2-methyl-2-butinal, 8-acetoxycetoxy-2
, 6-dimethyl-2,6-octagenal and 8-benzyloxy-2,6-dimethyl-2,6-octagenal are known to be produced by the following method.

(1) Rearrangement of 1,1-dimethoxy-2-methyl-3-butene in 2-acetate in the presence of copper(I) chloride to obtain 4-7cetoxy-1,1-dimethoxy-2-methyl -Production method of 4-acetoxy-2-methyl-2-butynal comprising hydrolyzing 2-butene: (Refer to JP-A-55-55140) +21 1.4
-Diacetoxy-2-butene is reacted with hydrogen and -carbon oxide in the presence of a rhodium catalyst, and the resulting 1,4-diacetoxy-2-formylbutane is thermally decomposed to produce 4-acetoxy-2-methylenebutanal. and then isomerizing the 4-acetoxy-2-methylenebutanal: (Refer to JP-A-51-146413) +31 3.
7-dimethyl-2.8-acetoxy-2, by oxidizing 6-octacyenyl acetate with selenium dioxide.
Production method of 6-cymethyl-2,6-octagenal: [Tetrahedro R7-L/Taz (Tetrahedro
nLetters) 1973, No. 281-28
See page 4] (8-benzyloxy-2, by using the addition reaction product obtained by reacting 413,7-dimethyl-2,6-octacyenylpenzyl ether with benzenesulfenyl chloride as a synthetic intermediate, 6-
Method for producing cymethyl-2,6-octagenal: and [Tetrahedron Letters]
Letters) 1978, No. 4539-454
See page 2] [The electrical point to be solved by the invention] The above conventional method has problems in industrially producing oxoterpene alcohol ffl. 2-acetoxy-1,1-dimethoxy-2-methyl-3-butene used as a raw material in the method (1) above is difficult to obtain industrially. In the method (2) above, 1,4-diacetoxy-
The reaction conditions employed in each reaction step are relatively harsh, such as the need to carry out the reaction of 2-butene with hydrogen and -carbon oxide under high pressure of 30 atmospheres or more. the above(
In method 3), selenium dioxide used in large amounts is highly toxic and sublimable, so FMH care must be taken when handling it. Furthermore, benzenesulfenyl chloride used in the method (4) above is expensive.

Therefore, one of the objects of the present invention is to provide a novel compound that can be easily produced from inexpensive and easily available industrial raw materials and that can be easily derived into oxine terpene alcohols in good yields. It is in. Another object of the invention is to provide a method for producing the new compounds.

[Means for solving problems]

According to the present invention, the above object is achieved by providing aminooxyterpene alcohols represented by the general formula (Il), and also by providing aminooxyterpene alcohols represented by the general formula (Il), in which B4 represents a lower alkanoyl group or a benzyl group, and Bz , H3 and n are as defined above) is reacted with an organic peracid or hydrogen peroxide, and the resulting product is heat-treated to produce a compound of the general formula (1112, B3, W and n are as defined above)), and then the amino xyterpene alcohol derivative is hydrolyzed as necessary. This is achieved by providing a method for producing aminooxyterpene alcohols shown in I).

Examples of lower alkanoyl groups represented by R+ and 134 in the above general formula include formyl group, acetyl group, propionyl group, and butyryl group, and examples of lower alkyl groups represented by L2 and B3 include methyl group, ethyl group, and p9. Examples include pyl group, isopropyl group, butyl group, and isobutyl group.

Examples of aminooxyterpene alcohols represented by general formula (I) include 4-(dimethylaminooxy)
-3-Methyl-2-buten-1-ol, 4-(dimethylaminooxy)-3-methyl-2-butenyl acetate, 4-benzyloxy-1-(dimethylaminooxy)-2-methyl-2 -butene, 8-(dimethylaminooxy)-3゜7-dimethyl-2,6-octacyene-1
-ol, 8-(dimethylaminooxy)-3,7-dimethyl-2,6-octazininyl acetate, 8-benzyloxy-1-(dimethylaminooxy)-2,6-
Cymethyl-2,6-octadiene, 3,7-cymethyl-8-(1-pyrrolidinyloxy)-2,6-octarenin-1-ol, 3,7-cymethyl-8-(1-pyrrolidinyloxy)-2 , 6-octagenylacetate and the like.

The general formula (
The aminoterpene alcohol derivative represented by m includes 2-(dimethylamino)-3-methyl-3-butenyl acetate, N,N-dimethyl(2-pencyloxy-
1-Impropenyl)amine, 6-(dimethylamino)-3,7-dimethyl-2,7-octazinylacetate%N,N-dimethyl(6-benzyloxy-1-impropenyl-4- methyl-4-hexenyl)
Amine, 3,7-dimethyl-6-(1-pyrrolidinyl)
Examples include -2°7-octarenin-1-ol, 3,7-dimethyl-6-(1-pyrrolidinyl)-2,7-octadininyl acetate, and the like. The aminooxyterpene alcohol derivative represented by the general formula (II) can be obtained by reacting the aminoterpene alcohol derivative represented by the general formula (II) with an organic peracid or hydrogen peroxide and heat-treating the resulting product. . Examples of organic peracids include aliphatic organic peracids such as peracetic acid, 1 perbenzoic acid, m
- Aromatic organic peracids such as chloroperbenzoic acid are used.

In addition, hydrogen peroxide can be used in its aqueous solution,
For example, it is convenient to use a commercially available 30% aqueous solution as it is. The organic peracid and hydrogen peroxide are usually used in an amount of about 1 to 2 mol, particularly about 1 to 1.2 mol, per 1 mol of the aminoterpene alcohol derivative represented by the general formula (m). The reaction between the aminoterpene alcohol derivative represented by the general formula (II) and the organic a-acid or hydrogen peroxide is carried out in the presence or absence of an organic solvent. For example, lower aliphatic alcohols such as methanol and ethanol; lower aliphatic carboxylic acids such as methyl acetate, ethyl acetate, and methyl propionate; Alkyl ester: methylene chloride, 1
, 2-dichloroethane, chloroform, carbon tetrachloride, etc.; organic solvents that do not inhibit the reaction, such as linear or cyclic ethers such as diethyl ether, silylable bile ether, and tetrahydrofuran, can be used. . The reaction temperature is usually -100°C to about 30°C.
℃ range, particularly about -70℃ to about 20℃ is preferred. The product obtained by this reaction can be separated from the reaction mixture, for example, by the following method.

A crude product can be obtained by mixing the reaction mixture with a basic aqueous solution such as an aqueous sodium hydrogen carbonate solution, extracting with ethyl acetate-methylene chloride, diethyl ether, etc., and distilling off the solvent from the extract.

The heat treatment of the product obtained by the reaction of the aminoterpene alcohol derivative represented by the above general formula (I[) with an organic peracid or hydrogen peroxide is carried out in the presence or absence of a solvent. As a solvent, methyl acetate, ethyl acetate,
Lower alkyl esters of lower aliphatic carboxylic acids such as methyl propionate; does not have any adverse effects on heat treatment of chlorinated hydrocarbons such as methylene chloride, l,2-dichloroethane, chloroform, and carbon tetrachloride. Organic solvents can be used. In this case, the general formula (III
The extract containing the product obtained by extracting the reaction mixture with the aminoterpene alcohol derivative r1m pseudohydrogen oxide with an organic solvent as described above can be subjected to heat treatment. Be practical.

The heat treatment is typically carried out at a temperature in the range of 40-150°C. The aminooxyterpene alcohol derivative represented by the general formula (2) obtained by the above heat treatment can be subjected to a purification operation such as column chromatography after distilling off the solvent from the reaction mixture, if necessary. It is obtained separately by

The aminooxyterpene alcohol derivative represented by the general formula Y thus obtained is hydrolyzed, if necessary, to convert it into an aminooxyterpene alcohol represented by the general formula +11.

That is, the aminooxyterpene alcohol derivative in which B4 is a lower alkanoyl group in the general formula (I) can be prepared by hydrolyzing it according to a known method for hydrolyzing a carboxylic acid ester, if necessary.
In this step, 341 is converted to an aminooxyterpene alcohol in which 341 is a hydrogen atom.

The hydrolysis reaction is typically carried out in an aqueous solution of an alcohol such as methanol or ethanol in the presence of a base such as an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide at a temperature ranging from 0 to 100°C. .

The aminooxyterpene alcohols obtained in the general formula tI) in which lil is a hydrogen atom can be separated and purified from the reaction mixture, for example, by the following method. The reaction mixture is extracted with ethyl acetate etc. after being mixed with water if necessary, the solvent is distilled off from the extract, and the residue is subjected to a purification operation such as column chromatography to obtain the general formula (Il Aminooxyterpene alcohols in which B1 is a hydrogen atom can be obtained.

The aminoterpene alcohol derivative represented by the general formula (II) is represented by the general formula (wherein B5 represents a hydrogen atom, a lower alkanoyl group, or a benzyl group, and n represents O or 1). The chloroterpene alcohols represented by the general formula (wherein L5 and n are as defined above) are obtained by reacting the terpene alcohols represented by the formula with hypochlorous acid, and then the chloroterpene alcohols are reacted with the general formula (wherein B2 and Il3 are as defined above) to obtain a general formula (wherein E2, B3=B' and n are as defined above). It can be obtained by esterifying aminoterpene alcohols as required.

The reaction between the terpene alcohols represented by the general formula
trahedron Letters), 1980, pp. 441-444.

e In the reaction between the chloroterpene alcohol represented by the formula Mf and the secondary amine represented by the general formula (■), the amount of secondary amine is usually about 1 mole per mole of the chloroterpene alcohol represented by the general formula (■). Used in more than 30 minutes. The reaction temperature can be usually selected within the range from θ°C to the boiling point of the secondary amine, but a range of about 20 to 50°C is particularly preferred. The reaction is carried out in the presence or absence of a solvent, such as water; lower aliphatic alcohols such as methanol and ethanol; nitriles such as acetonitrile;
Solvents that do not adversely affect reactions such as amides such as N,N-dimethylformamide can be used alone or in combination. Further, by using the secondary amine in a large excess amount relative to the chloroterpene alcohol represented by the general formula (V), the secondary amine can also serve as a solvent. In addition, when the reaction between a chloroterpene alcohol in which l in the general formula (■) is a lower alkanoyl group and a secondary amine represented by the general formula (■) is carried out in the presence of water, a hydrolysis reaction occurs. Thus, an aminoterpene alcohol having the general formula (Vl) in which B5 is a hydrogen atom, or a mixture of the aminoterpene alcohol and an aminoterpene alcohol having the general formula (2) in which R5 is a lower alkanoyl group is obtained.

The aminoterpene alcohol represented by the general formula thus obtained can be separated and purified from the reaction mixture, for example, by the following method. The reaction mixture is
For example, it is mixed with a basic aqueous solution such as an aqueous sodium hydroxide solution, extracted using a solvent such as diethyl ether, ethyl acetate, or benzene, the solvent is distilled off from the extract, and the residue is subjected to purification procedures such as column chromatography. Aminoterben alcohols represented by the general formula (2) can be obtained by subjecting the compound to the following.

The aminoterpene alcohol represented by the general formula (2) thus obtained is converted into an aminoterpene alcohol derivative represented by the general formula (TI) by subjecting it to esterification as necessary. That is, in the -ff formula ■, B
By esterifying aminoterpene alcohols in which 5 is a hydrogen atom with a lower alkanoic acid or a reactive derivative thereof according to a known method for esterifying ordinary alcohols, ill is a lower alkanoyl group in the general formula fIIl. Converts to aminoterpene alcohol derivatives. For example, an aminoterpene alcohol in which B5 is a hydrogen atom in the general formula (2) is prepared in a solvent such as pyridine or triethylamine in an amount of acetyl chloride or propionyl chloride in an amount of usually 1 mol or more per 1 mol of the aminoterpene alcohol. By reacting with a lower alkanoic acid chloride such as or a lower alkanoic anhydride such as acetic anhydride or propionic acid decoction, an aminoterpene alcohol derivative in the general formula fIl) in which B1 is a lower furucyl group can be obtained. The reaction of aminoderpene alcohol derivatives in which B1 is a lower alkanoyl group in the general formula flIl obtained by esterification of aminoterpene alcohols having a five-force hydrogen atom in 11 to the general formula thus obtained Separation from a mixture - Mix with a thin solution, etc., extract with diethyl ether, etc., dry the extract with anhydrous magnesium sulfate, etc., distill off the solvent from the dry solution, and purify the residue using column chromatography. By attaching to the general formula (
In II), an aminoterpene alcohol derivative in which Bl is a lower alkanoyl group is obtained.

The aminooxyterpene alcohols represented by the general formula (m) of the present invention can be converted into the oxoterpene alcohols represented by the general formula (2) in good yield, for example, by the following method.

Alkyl halide or allyl pear halide h30H
3 0=ufII-0=011-CL[2(-(,B2-U
WOB-On, -), 0-R1(Vllll (B in the above formula
1, B2 R3 and n are as defined above), i.e., dithylhen alcohols represented by the general formula (Il), alkyl halides such as methyl iodide, ethyl bromide, propyl butyl chloride; or Allyl chloride, allyl bromide, allyl iodide, l-chloro-3-
By reacting with an allyl halide such as methyl-2-butene, oxoterpene alcohols represented by the general formula (2) can be obtained.

In addition, aminooxyterpene alcohols in which ljl in the general formula (I) is a lower alkanoyl group or a benzyl group can be prepared by contacting it with zinc in the presence of an acid to obtain the aminooxyterpene alcohols of the general formula % formula % (1) (in the formula BT represents a lower alkanoyl group or a benzyl group, and n is as defined above), and the diol derivative is converted to manganese dioxide,
Oxoterpene alcohols in which B1 is a lower alkanoyl group or benzyl group in the general formula (2) are derived by oxidation using a known oxidizing agent commonly used in the oxidation reaction of alcohols such as chromic anhydride to aldehydes. be done.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited by these Examples.

Reference example 1 H20 α N (0H3)2 N (0H3).

Dissolve 50.0 g (0,324 mof) of 3.7-dimethyl-2,6-octarenin-1-ol in 2.71 methylene chloride and add 300 r of saturated aqueous sodium sulfate solution.
42 g of bleached powder (available chlorine 61%) were added, and dry ice was added in small portions (10 g) to this mixture while maintaining the reaction temperature below 10°C.
Add dry ice pieces 10 times at 10 minute intervals,
0 g dry ice pieces were added nine times at 10 minute intervals). After addition of dry ice, continue stirring roughly for 2 hours while maintaining the reaction temperature below 10°C. A white precipitate was separated from the resulting reaction mixture, and an organic layer was separated from the P solution.

This organic layer and the extract obtained by extracting the aqueous layer with methylene chloride were combined, and the mixture was added with anhydrous magnesium sulfate for 30 minutes.
It took 0 minutes to dry. Methylene chloride was distilled off from the dry liquid under reduced pressure to obtain 63 g of residue. This Qfi is N
Analyzed by MB spectrum, the purity was 81%.
-Chloro-3,7-dimethyl-2,7-octarenine-
1-ol (Yield: 83%) 6 6-Chloro-3,7-dimethyl-2 with a purity of 81% as described above
．． 1.85g of 7-octarenin-1-ol (
7,95 mol) was added to a mixed bath solution of 20 WLl of a 50% dimethylamine aqueous solution and 7RRLl ethanol, and stirred at room temperature for 7 days. Dimethylamine and ethanol were distilled off from the resulting reaction mixture under reduced pressure, and 0.5 g of sodium hydroxide and 30 yn of water were added to the residue.
After adding a solution consisting of J, the mixture was extracted with ether. The extract was dried over anhydrous magnesium sulfate and then subjected to S-condensation under reduced pressure. The residue was subjected to silica gel column chromatography [eluent: ethyl acetate/hexane (volume ratio) x 1
/9 to 2/8], 1.14 g of 6-(dimethylamino)-3,7-dimethyl-2.7-octarenin-1-ol was obtained (6-chlorof2-3 .7-dimethyl-2,7-octarenine-1-
yield near 3%).

@-NMIi (GO(14/TM8) δ: 1.63
(6u, S), 1.6-2.2 (4H, m), 2.13
(6if, ri, 2.30 (IH, t, J=7fIz),
3.33(111,b8), 3.93(2f(,d,J
=7Hz), 4.73(2L(, bs ), 5.23(
1)1. t, Jx7Hz) LH (film): 3350.1440.1370.
1020.890α-1 6-(dimethylamino)-3,7-dimethyl-2゜7-
Octarenin-1-ol 1.14 g (5.8 mmo
1) in 2rrLl of pyridine, and 1.1ml of acetic anhydride.
After 25 g (12.3 minol) was gradually added dropwise at room temperature, stirring was continued for 2 days. After the reaction is complete, water and a saturated aqueous sodium hydrogen carbonate solution are added to the reaction mixture.
Afterwards, the mixture was extracted with ether, and the extract was dried over anhydrous magnesium sulfate. After distilling off the solvent from the dried liquid under reduced pressure, the residue was subjected to silica gel column chromatography [elution? l
f: ethyl acetate/hexane (volume ratio) = 1/9 to 515
] and purified with 1.2:1 g of 6-(dimethylamino)-3,7-dimethyl-2,7-octazininyl acetate.
[Yield based on the 6-(dimethylamino)-3,7-dimethyl-2.7-octarenin-1-ol used: 89%].

'H-NMR (ecJ, /TM8) δ: 1.65.
1.70 (each3LL, !11; 1.60-2.
00 (4H, m); 1.97 (31i, S
) ; 2.15 (61i, s ) ; 2.42 (In
, t, J-6Hz); 4.50 (2n, d,
J-711z) i4.85 (2EL, m) i5.2
9 (IH, t, J=7Hz I II ((film)): 1740.1450% 137
0.1235.1020.900CII-' Example 1 N(OH3)2 6-(dimethylamino)-3,7-dimethyl-2゜7
- octadininyl acetate 1.0 g (4.2 mm
After adding 0.49 g of sodium carbonate to a solution of 01) and 30 ml of methylene chloride, 88 g of a mixed solution of peracetic acid, acetic acid and water containing 40ijd% peracetic acid was prepared at a temperature of -60°C with stirring. Peracetic acid (4.6 mmol) was gradually added dropwise. After completing the dropwise addition, stirring was continued for 30 minutes at a temperature of -60°C, and then the temperature was gradually raised to 0°C. Saturated sodium bicarbonate was added to the heated reaction mixture,
After adding aqueous solution, f2!5ynll, the organic layer was separated,
Extract the aqueous layer with ethyl acetate. The F3 layer and the extract were combined and dried over anhydrous magnesium sulfate.

The obtained dry liquid was heated at a temperature of 50°C for 1 hour. After the heat treatment, the solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography [eluent: ethyl acetate/hexane (volume ratio) = 1/9 to 2/8]. -(dimethylaminooxy)-3,7
-Simethyl-2,6-octadininyl acetate at 0.
Obtained 92 g [6-(dimethylamino)-3 used]
, 7-dimethyl=2.7-octadininyl acetate yield: 86%].

'H-NMl((CCl4/TK8)δ: 1.6
3, L70 (each: Hl, S);1.
97(:01.S)il, 88~2.28(4R,m
)B2. s.

(6R, s); 3.97 (2U, 3); 4.53 (2H
, d, J===7Hz) i 5.35 (2H,
t, J=7)1z)I)1(film)shi:1
740.1440.1380.1230.1120cm
” Reference Examples 2-3 N (CL(3).

In Reference Example 1, 3,7-dimethy/L/- instead of 3,7-dimethyl-2,6-octarenin-1-ol
2.6-octazinylbenzyl ether or 3-nonal-2-butenylbenzyl ether [each with the general formula σ
(corresponds to terpene alcohols in which B5 is a benzyl group and n is 1 or O)] at 0.324v
A chloroterpene alcohol in which B5 is a benzyl group and n is 1 or O in the general formula (2) was obtained by performing the reaction with hypochlorous acid and separating the reaction product in the same manner except that naL was used. Obtained. Then, 7.95 rnmol of the nine chloroterpene alcohols obtained
The reaction operation with dimethylamine and the separation operation of the reaction product were carried out in the same manner as in Reference Example 1 except that 6-chloro-3,7-dimethyl-2,7-octarenin-1-ol was used, An aminoterpene alcohol derivative having the general formula (Ill) in which B4 is a benzyl group and n is 1 or O was obtained. Table 1 shows the ratio (value based on the chloroterpene alcohols used) and the results of instrumental analysis.

Reference example 4 Cn2=ccuc1i, cu2c=ei-tea2o
coca3○ In Reference Example 1, 3.7-dimethyl-2.
63.5 g (0,324
The reaction with hypochlorous acid and the separation of the reaction product were carried out in the same manner except for using 66.31 pieces of tart were obtained (yield near 9%).
). Then, such 89% pure 6-chloro-3,7-
40 g (0,154 mol) of cymethyl-2.7-octadieny/reacetate, 62 g of pyrrolidine
, 55g of sodium carbonate and 500yn of acetonitrile
J was mixed and heated under reflux for 16 hours. The resulting reaction mixture was filtered under suction, and pyrrolidine and acetonitrile were distilled off from the filtrate under reduced pressure. A saturated aqueous sodium bicarbonate solution was added to the residue, followed by extraction with ether, and the extract was dried over anhydrous magnesium sulfate. The solvent was distilled off from the dry solution under reduced pressure, and the residue was subjected to silica gel column chromatography [eluent: ethyl acetate/hexane (volume ratio) -2/8~
1O10] to obtain 13 g of 3.7-dimethyl-6-(1-pyrrolidinyl)-2°7-octazininyl acetate (using 96-chloro3.7
-Yield based on 2.7-octadinyl acetate: 32%).

'11-NMH (CCl4/TM8) δ: 1.67 (
6R, bs), 1.5-2.2 (9H, m), 1.9
5 (3i1.m), 2.1~2.6 (411°+n
), 4.45 (2n, d, J=7nz ), 7.76 (
211,11), 5.23 (LH, t, J=7112) In (film) )/ : 1740.1370.1
240.11203-'Examples 2 to 4 In Example 1, 6-(dimethylamino)-3,7-
The same procedure was followed except that 4.2 rnmol of an aminoterpene alcohol derivative having the general formula (in m, H2, H3, H4, and n were as shown in Table 2) was used instead of dimethyl-2,7-octazininyl acetate. In the general formula + I), Bl, l(Z, 1 (values based on aminooxyterpecol 3#! body, where 3 and n are shown in Table 2) and analysis results were obtained. Shown in Table 2.

Example 5 N (el13)2 6-(dimethylaminone-3,7
-Simethyl-2,7-octacyenyl acetate was reacted with peracetic acid. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic ta and the extract were combined, and this mixture was dried over anhydrous magnesium sulfate, and then heated at 5oC for 30 minutes.
After heating for 9 minutes, the solvent was distilled off under reduced pressure,
8-(dimethylaminooxy)-3,7-dimethyl-2
1.05 g of a crude product containing ゜6-octadininyl acetate as a main component was obtained.

This crude product was dissolved in an aqueous methanol solution [methanol/water (volume ratio) = l o/l) 20 mJ', 0.81 g (5.9 mtnoI) of potassium carbonate was added, and the mixture was stirred at room temperature for 1.5 hours. 50% of water was added to the obtained nfC reaction mixture, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography [eluent: ethyl acetate/hexane (volume ratio) -1/
9 to 2/8] to obtain 0.54 g of 8-(dimethylaminooxy)-3,7-dimethyl-2.6-octarenin-1-ol [the used 6-(dimethylamino)- : Yield based on 4,7-dimethyl-2,7-octadininyl acetate: 61%].

ll1-Null (006,/TM8) δ: 1.6
2(61i,!1)il, 93-227(4H,rn)
;2.12(6n,s);3.72(114°bs)
H3,88(211,a);3.93(2Li,d,J
=6Hz) H5,22 (2kL, t, J=6
jlz ) Il Book (Film) C: 3350.1690
．． 1440.13 HO.

1020C111-' Example 6 N (an3).

6-(dimethylamino)-3,7-dimethyl-2゜7-
Octadininyl acetate 1.0 g (4,2 mmo
l) and 30 parts of methanol at room temperature with stirring.
% hydrogen peroxide solution (1,476g (4.2mtnoI
) was gradually added dropwise, and stirring was continued for 30 minutes at room temperature even after the addition was completed. The resulting reaction mixture was poured into water and extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate.

The obtained dry liquid was heated at a temperature of 50°C for 1 hour. After the heat treatment, the solution was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography [eluent: ethyl acetate/hexane (volume ratio) = 1 ml 10/cs) - r% 4
% 1li11-)-17k ly” Tori Ding Q -t
:S methylaminooxy)-3, two-dimethyl-2,
0.54 g of 6-octadinylacetate was obtained [using 6-(dimethylamino)-3,7-dimethyl-2].
．． Yield based on 7-octacyenyl acetate: 51%
). The analysis results of this product were in good agreement with the analysis results obtained in Example 1.

Reference Example 5 8-(dimethylaminooxy)-3,7-dimethyl-2,6-octadininyl aceter ho, 50 g (2,0
mmol) in 15TnJ of chloroform, and add 1.04g of tetrabutylammonium iodide to this solution.
(0,1mtnoI) and allyl bromide 4.7
After adding g (40 mrnol), the mixture was heated under reflux for 4 hours. The reaction mixture was poured into 50 ml of water, and then diluted with 100 ml of diethyl ether.
The extract was dried over small amounts of magnesium sulfate, and the solvent was distilled off from it under reduced pressure.

The obtained residue was subjected to silica gel column chromatography [eluent: hexane/ethyl acetate (volume ratio) = 9/
1 ], 8-acetoxy-2,
6-cymethyl-2.6-octagenal 0.34 g
was obtained (yield: 83%).

Reference example 6 H3CH3 1l Zn (t3L13)2N-0-Cn, c=enca, Cn2
e=ciicn2ococn3-→1.0 Q of zinc powder washed sequentially with 5% hydrochloric acid, water, methanol and ether and then dried was converted into 8-(dimethylaminooxy)-3,7
-Simethyl-2.6-octadininyl acetate 0.3
0 g (1.2 mrnol) was added to a mixed solution consisting of 15 ml of vinegar and 15 ml of water, and the mixture was stirred at room temperature for 24 hours. 40 ml (l) of water and 50 ml of chloroform
Method I was performed sequentially on m1.

The obtained F# liquid and the washing liquid were combined, neutralized with sodium carbonate, and then extracted with chloroform. After drying the extract with sodium carbonate, the solvent was distilled off under reduced pressure to obtain 8-7 setoxy-2,6-dimethyl-2,6-
0.247 g of octarenine-1-olda was obtained (yield:
quantitative).

〔Effect of the invention〕

According to the present invention, as is clear from the above examples, aminooxyterpene alcohols represented by the general formula +I) are produced from inexpensive and easily available industrial ingredients. Further, oxoterpene alcohols can be easily derived from aminooxyterpene alcohols represented by the general formula (Il) in good yields.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 represents a hydrogen atom, a lower alkanoyl group, or a benzyl group, and R^2 and R^3 are represents a lower alkyl group or together represent a tetramethylene group,
n represents an integer of 0 or 1). 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^2 and R^3 represent a lower alkyl group or together represent a tetramethylene group, and R^4 is a lower alkyl group. (represents an alkanoyl group or a benzyl group, and n represents an integer of 0 or 1) is reacted with an organic peracid or hydrogen peroxide, and the resulting product is heat-treated to produce the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(III) (In the formula, R^2, R^3, R^4 and n are as defined above) An aminooxyterpene alcohol derivative represented by the formula is obtained, and then the amino A general formula characterized by hydrolyzing an oxyterpene alcohol derivative as necessary ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1 represents a hydrogen atom, a lower alkanoyl group, or a benzyl group. , R^2, R^3 and n are as defined above) A method for producing aminooxyterpene alcohols.