JPS588034A - Optically active tetrahydronaphthalene derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:An optically active compound of formulaI(R is alkyl). EXAMPLE:Optically active 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene. USE:Perfume: it is characteristically different from the racemic isomer kanonw as a musk perfume and no discoloration occurs even which it is mixed with other perfumes. PREPARATION:The reaction between an optically active isomer of formula III (pyrosin) and a compound of formula IV, when necessary, in the presence of an acid catalyst, is followed by treatment with a Friedel-Craft catalyst to form an optical active isomer of formula II. The decarboxylation is effected and the resultant optically active isomer of formula V is acetylated to give the optically active isomer of formulaI. Its (-)-isomer (S) has stronger musk odor than (+)- isomer (R) and racemic isomer and further it smells more refined, while (+)- isomer has a light and sweet smell.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel optically active tetrahydronaphthalene conductor and a method for producing the same.

More specifically, the present invention relates to an optically active tetrahydronaphthalene derivative represented by formula (I*) that is useful as a fragrance and the 7OIl method.

(In the formula, R represents an alkyl group.) In the metal compound O represented by the formula (I*), R is a methyl group, and! 17-7 Sechiru/, /, J, Da, Da.

4-Hexamethyl-/5JeJe'G'-tetrahydronaphthalene is a synthetic fragrance known under the popular name ``Tonalin R'' and has a musk-like fragrance that is valuable in the fragrance O area, and is an important synthetic fragrance. It is a type of fragrance.

l! Tetralin-based musk, which replaces natural macrocyclic ketone-based musk fragrances, is superior in quality, retention, and safety! tK superiority** has increased tremendously.

The synthesis method for TonaVyF uses a precursor.

1.3. Da, da, 4-Heki! Methyl-/, 1゜3, l-
A common method is to acetylate tetrahydronaphthalene (hereinafter abbreviated as HMT) (Journal of Organic Chemistry: J, Org, Che
z, 2 F, 2.2'll (/riA
J)). Various methods are known for the synthesis of HMT. A method of reacting with (nap 41f!'/, 60/ ;u @
P 3.2'H, u) or 3.3-dimethyl-/
- A method of reacting with butene in the presence of activated clay or a cation exchange resin (asp J, 77?, 7zada; usp 3,37ri, 7ffj), etc., ■, 2
- (p -') u"Jk) - A method of reacting -,2-halogenated propane and neohexene in the presence of aluminum chloride (usp4J Buddha, Burial, ■ Using p-cymene as a raw material, λ, 3-dimethyl A method of reacting 1-1-butanol or expanded 3,3-dimethyl-/-butene in the presence of an acid catalyst (Journal Opeorganic φK: J, Org, Ckwm II@λt=
63) or a method of reacting neohexene and tertiary alkyl halide in the presence of aluminum chloride O (USP &I!; 1) 176 and Tokko Shoj
3-100! ; Publication No. 7), etc.

By the way, regarding the tetralin derivatives represented by the general formula (gate), for example, Tonalid has /ke asymmetric carbon atoms in its molecule, so (+) integral (6) and (→ integral (8)
Although there are optical antipodes, the above-mentioned 9H production methods are all related to the tonalid. No optically active tonalide has been synthesized to date. On the other hand, from the perspective of an optically active substance, there are cases in which geokinobacterial Ka itself exhibits the characteristics of 11 due to its asymmetric structure, but in general, bioactive substances with an asymmetric structure Among the possible optical enantiomers, it is often a specific enantiomer that is useful to humans. Many examples of this are found in medicines, agricultural chemicals, pheromones, food additives, etc.

There are many examples of 41j1m in the fragrance field.For example, for the odor of peppermint, toll, and the odor of Japanese apricots, (→-carvone, grapefruit odor, Ka(+)-wing-tocatone, etc.) are useful. Moreover, it has been reported that the dextrorotatory carvone has the odor of cypress, and the levorotary carvone has the odor of cypress (Journal Eve 1). Je,
AJr*Food Chem,, / 9, 7J'
j (/tough/))O These either have a different odor from the other optical enantiomers, or have a strong odor. That is, the odor quality often differs depending on the enantiomer or from the racemate. Therefore, optical life! ! Developing members of the II family is of great significance as it will lead to the development of new odors or effective optical enantiomers as well as the development of new fragrances. In general, subtle differences in the smell of cosmetics and the like have a large impact on the product. Creating a new odor based on the optical activity of this rounded synthetic fragrance is a great opportunity to bring about great progress in the fragrance world.The method for obtaining the optically active tetrahydronaphthalene derivative represented by the general formula (1'') is by racema. A method of optically resolving the target material is considered.However, optical resolution is generally difficult except for those having functional groups such as carboxyl groups and amino groups.

However, by discovering a new method for optically active tetrahydronaphthalene derivative OII represented by the formula (1), the present inventors succeeded for the first time in synthesizing the desired optically active tetrahydronaphthalene derivative, and demonstrated its great utility. admitted.

The manufacturing method is optically active Q-(,2-methylpropenyl)
-5,! ;-Dimethyl-tetrahyFO furanone (commonly known as pyrosine) and alkyl-substituted benzene are reacted in the presence of a Friedelkraff catalyst, or pyrosine and alkyl-substituted benzene are reacted! ! This is a completely new method consisting of reacting with 11 reactions, postmortem, Friederclay followed by decarboxylation to obtain an optically active tetrahydronaphthalene derivative represented by the formula (-), and acetylating this. represents an alkyl group.) CHJ ca3 can be produced. Thus, the original lj! This will lead to the development of nine fragrances that have different aromas from (g)-tonarid and (to)-tonachit, which are produced by s, and have new values that are different from conventional (e)-tonarid. In other words, about the scent of Tonarid's antipode.
) Hetai (Q has a strong odor as a musk (→ Hetai (6)) It has a strong racemic scent, and has a natural scent, but is elegant and has excellent retention.Also (+ ) together (6
) is light and has a sweet aroma. These nine properties do not cause discoloration even when used in combination with other aromatic chemicals, such as soaps, cosmetics, household products, smoked perfumes, or alcoholic liquids such as Rosi. do not have.

Next, the manufacturing method of the present invention will be explained separately into the manufacturing method of the compound represented by the formula (1'), the compound represented by the formula (Ill''), and the compound represented by the formula (1'').

By reacting rosin and aromatic hydrocarbon in the presence of a Friedelkraff catalyst, the optically active pyrosine can be produced in one step in a high yield under mild conditions. (Agricultural Chemistry and Biological Chemistry; Agr, Elol, Ch@w,, J ￥
.

//B; (/270)).

Aromatic hydrocarbons include toluene, ethylbenzene,
Furkyl-substituted benzenes such as propylbenzene and butylbenzene are used.

As a Lewis acid effective for promoting this reaction, those generally used in the Friedel-Crach reaction, such as L1 ferric aluminide chloride, are used. The amount used is usually 7.5 molar equivalents to 7.5 molar equivalents, preferably 1 molar to 7.2 molar equivalents. When carrying out the method of the present invention, it is also possible to use a solvent that does not essentially inhibit the reaction. It is possible to use a large amount of aromatic hydrocarbon in advance so that it also serves as a solvent.

The reaction temperature is usually -JOC to below the boiling point of the aromatic hydrocarbon, which is sufficient. In order to suppress the production of isomers in this reaction, it is preferable to lower the reaction temperature, and the temperature FrL is 1/
QC to J□C are practical.

The reaction time varies depending on the reaction conditions, but is usually 5 minutes to 1 hour.
You can reach your goal in 0 hours. The progress of the reaction can be determined by collecting a portion of the reaction solution and analyzing it by gas chromatography, thin layer chromatography, etc. It can also be obtained by reacting with an acid catalyst to form a new lactone compound (1''), followed by treatment in the presence of a Friedel-Craft catalyst.

As shown in the figure, it is as follows.0 As the acid used in this reaction, acids such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and naphthalenesulfonic acid can be used as a catalyst.

When carrying out this reaction, it is possible to use a solvent that does not essentially inhibit this reaction, or it is also possible to use a large amount of aromatic hydrocarbon in advance to also serve as a solvent. The reaction temperature is usually -30C to below the boiling point of the aromatic hydrocarbon, which is sufficient. Then, the following reaction can be carried out with or without isolating the generated compound represented by the general formula (1"). That is, the amount of lactonization represented by the general formula ff") is reduced by the general formula The catalyst and reaction conditions used in producing the compound indicated by (-) are the same as in the one-step production method described above.

As mentioned above, if optically active pyrosine is used in this reaction, the compound represented by the formula (l*) produced also has optical activity, and the optical activity is maintained. For example, in the case of reaction with toluene, dextrorotatory pyrosine (ethanol 11%
) $ are the dextrorotatory product (benzene solvent), and the levorotatory product (e) is from the levorotatory pyrosine (ethanol solvent).
benzene solvent) is obtained.

The product thus obtained can be highly purified by ordinary isolation procedures, but if necessary, it can be purified by means such as recrystallization or chromatography.

(c) Method for producing a compound represented by formula (1') A compound represented by formula (-) is decarboxylated to produce a compound represented by formula (I*). Various methods can be used for decarboxylation, including the following method of halogenation decarboxylation followed by reduction. The diagram is as follows.

or'') (r town (?) As an example of the halogenated decarboxylation method, there is a method of heating the compound & (hereinafter abbreviated as carboxylic acid) represented by the formula (-) in the presence of lead tetraacetate and alkali metal parite. It will be done.

That is, by heating the carboxylic acid in the presence of lead tetraacetate and an alkali metal halide, the halogenation and decarboxylation reaction easily proceeds, and the desired compound (11) is obtained. More specifically, when carrying out this reaction, it is preferable to dilute with a solvent that does not essentially inhibit this reaction. Examples of such solvents include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, and
Examples include setonitrile. Examples of the t+ alkali metal halide include sodium chloride, potassium chloride, lithium chloride, lithium bromide, and lithium iodide, with lithium chloride being preferred. The reaction temperature is usually from room temperature to /4t07:, preferably from 70C to 100C.
It is.

The amounts of lead tetraacetate and alkali metal halide (for example, lithium chloride) used in this reaction are theoretically equivalent to 1 mole of the carboxylic acid to be treated. It is also possible to use an excess amount of I11 tetraacetic acid to increase the reaction rate.
For example, it is 1 times the mole or less. Using more than this is not a good idea as it may promote side reactions.

However, if the production of by-products is to be suppressed as much as possible and the selectivity of the target product is to be increased, it is possible to use less than a molar amount.

Use of purified Nenshizusun lead gives even better results. As mentioned above, the amount of alkali metal halide is theoretically required to be equivalent to 1 mole of carboxylic acid to be treated, but it can be used in excess to increase the reaction rate, or it can be used in excess to increase the selectivity. If so, less than this molar amount may be used. It is usually 7,j to 0 times the amount of lead tetraacetate that is incorporated.

The reaction time can vary depending on the reaction conditions, but typically 30 minutes can be suitable for io waiting purposes. The progress of the reaction can be determined by analytical means such as gas chromatography, thin layer chromatography, chromatography, and NMR spectroscopy. After removing inorganic compounds such as lead diacetate from the reaction solution, the compound of the present invention can be obtained by concentrating the solution. If necessary, it is also possible to purify by conventional means such as extraction, distillation, and chromatography.

By hydrogenolyzing the halide thus obtained, an optically active tetrahydronaphthalene derivative 1c represented by the formula (-) can be derived. Hydrogenolysis methods include methods using metal hydrides, Examples include methods such as catalytic hydrogenolysis.As for metal hydrides, there are methods using lithium aluminum hydride or a combination of lithium hydride and lithium aluminum hydride.In this case, the compound represented by the above-mentioned Hikki?) is mixed with tetrahydrofuran, etc. It is sufficient to dissolve it in an ether, add lithium aluminum hydride, etc., and react at a temperature below the boiling point of the solvent normally used from QC.

The amount of lithium aluminum hydride used is determined by formula (II”)
The amount is usually 6 mol to comol, preferably 1 mol to 1 mol, per mol of halide. In the method based on the combination of lithium hydride and lithium aluminum hydride, the formula (for 7 moles of the halide in Hyo'cho, lithium hydride is 7 moles to 2 moles, lithium aluminum hydride r
A combination of ao, i mol to 0, 6 mol is preferably used.

The progress of warping can be determined by analytical means such as gas chromatography and thin layer chromatography.

The product has high purity as it is, but if necessary, it can be further purified by distillation or the like.

Further, examples of the catalytic hydrogenolysis method include a method in which hydrogen is reduced in the presence of a catalyst such as palladium or nickel. In particular, the reaction proceeds suitably by using a palladium-based catalyst. In this case, the reaction will proceed smoothly if about 1 molar of the base is present relative to the halide.

Examples of bases include organic acid salts of alkali metals (sodium acetate, potassium acetate, etc.), organic tertiary amines (triethylamine, pyridine, etc.), or amide compounds (N, N-dimethyl, N, M-diethyl, etc.). etc.)
is preferably used. When conducting the reaction, it is preferable to dilute the reaction as desired with a solvent that does not essentially inhibit the reaction. Examples of such solvents include alcohols such as ethanol, impropatol, and tertiary butanol, benzene, toluene, etc. aromatic hydrocarbons, and ethers such as tetrahydrofuran and dioxane.

The palladium-based catalyst used for this reduction reaction is
Both non-supported and supported types can be used. Moreover, they may be used as powders, or may be molded into appropriate shapes and sizes. Examples of unsupported catalysts used include palladium black, palladium oxide, and palladium chloride.

As supported catalysts, for example, palladium-charcoal, palladium-silica, palladium-alumina, etc. on various carriers may be used.0 Amount of palladium catalyst used f14I
Although Ka is not determined, it is 0.00/~/equivalent, preferably 0.0/~0.0/equivalent to 1 mole of raw material halide in case of batch reaction. The amount of insects.

The hydrogen used in the reduction reaction may be any ordinary commercially available hydrogen, and its use is not particularly limited as long as it is stoichiometric or higher for the purpose of simply completing the reaction, and the reaction will proceed even at normal pressure. A method of applying pressure is also used to promote the reaction. Normally, a temperature of /30 atm or less is sufficient.0 It is preferable to heat the reaction to the reduction reaction temperature in order to promote the reaction, but in order to suppress side reactions, the temperature is 100 C or less, preferably in the range of about 10 C to 10 C. is appropriate.

(3) Process for producing the compound represented by formula (1') Formula (I″l
) is acetylated to produce a compound represented by formula (1''). As the acetyl north method, the Friedel-Craf acetylation method can be adopted. That is, acetylation of acetyl chloride, ketene, acetic anhydride, etc. This is a method in which the acetylating agent is reacted in the presence of a Friedelkraff acylation catalyst such as aluminum chloride or ferric chloride. The acylation catalyst varies depending on the acetylating agent used, but when using 7cetyl chloride or ketene, it is 0 to 7.5 mol per 1 mol of acetylating agent, and when using acetic anhydride, it is 1 mol of acetic anhydride. 1.0 to 2.3 mol is used.

The reaction solvent may be a halogenated hydrocarbon such as dichloromethane/codichloroethane, nitrobenzene, carbon disulfide, or the like, which is used in a normal Friedel-Crafu acylation reaction.

The reaction temperature can be carried out below the boiling point of the solvent used, but preferably -1OC to 30C is employed. Although the reaction time varies depending on the reaction conditions, the objective can usually be achieved in 5 minutes to 10 hours.

The following examples explain the present invention vJ4 Example/Optically active 3-(Carbotei dimethyl)-7t/, da, lI
, a-pentamethyl-/, kot'? +Production method of di-tetrahydronaphthalene (1) (8)-Hiro-(comethylpropenyl)-5
゜j-Dimethyltetrahydrocofuranone ([α]
- Nico, 50 (oo, s, ethanol)) λ, s.

Dissolve g (iu, q mmol) in 30-g of toluene and add 10 g (iu, q mmol) of anhydrous aluminum chloride.
j) was added and stirred for S hours at /QC. /1 LII hydrochloric acid IOd was added and the mixture was separated and washed with diluted hydrochloric acid. The toluene layer was extracted with S thiammonia water, acid-precipitated with JO sulfuric acid, and extracted with toluene. After washing with saturated saline and drying with Glauber's salt,
Distill toluene under reduced pressure to give 7.7? g of product was obtained. (
[α), 4. -23. Heating the Io(0/, benzene)) product n-hex! After dissolving in the solution, the crystals K precipitated after cooling.
Separate F, concentrate Fiml, 3, g (/J, J mm
o), zzfb) H-JC carboxymethyl)-/
, /,tI,Q,4-pentamethyl-/,2,3. Q-
Tetrahydronaphthalene was obtained 0[α],46-m,-〇(〇hebenyne) NMR spectrum (0αy3) δ(pp-) = 10(3a,
g), 8λl (word-'), /, 34t (3H,a)
, Ko, 30 (3H, at ), 8#xJ, J',? (
jH, m), j, # ~7.3beta-), lλ, 17 (
la-) IR spectrum (at): /70! (0=0)
(J) (6)-der(comethylbrobenyl)1+
5-dimethyltetrahydro-2-furanone ([α]
+t here. °(a o, j, ethanol)) ko, s.

g(/da, 2mmo)), perform the same operation as in (1) of Example/(a) -, ? -(carboxymethyl)-/,/, da, da, 6-bentamethyl-/, ko, 3
．． Dirtetrahydrophthalene 3.3! g (/JJ
I got mmo), 74, h).

[α] +-6,3° (C/, benzene) 46 NMR and IR spectra were the same as those in Example/(1).

j-dimethyltetochydrocofuranone ([α]+t
ko, o0 (oo, se, ethanol) ) o, ysg
(O♂m+no/) t) Dissolved in 10- toluene, added 0.3-〇 concentrated sulfur #, and stirred at room temperature for 1 hour.

The toluene layer was washed with an aqueous sodium hydroxide solution, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to give 0,027 g (so-chi).
(s)-s, s-dimethyl-
p-rubro(0)-tetrahydrocofuranone was obtained.

[α), 6+ 3s, so (03.benzene to c) N
'MR(ODC!)3) δ(ppm)=to1a(Ja
,a),8JIF(jH,a),8,? 0 (AJa),
8go~/, ts(sm.

m), 2. ．． 21 (3H, m), 7.041 (41H,
a) IR(even) /740 The thus obtained (S)-S,S-νmethyluda-(comethyl-J-p-)rilp-bih)-tetrahydro-
Dissolve 2-7 lanone lOOkitt10d in toluene, /
Add 30If of anhydrous aluminum chloride, add 30If of anhydrous aluminum chloride,
After stirring for a minute, the fflo reaction solution was washed with dilute hydrochloric acid, dried, concentrated, and isolated to give fjlq (8) -,7-(carboxymethyl)-/, /e, da, da.

The O NMR spectrum of 6-pentamethyl-/eJs'*''-tetrahydronaphthalene was the same as that of Example 1 (1).

[α) +24.3° (O/, benzene) 46 Example optical activity 7. /, 3t da, da, 6-hexamethyl-1,
x, 3. Hiro-Production method of tetrahydronaphthalene (1) (6)-3-(carboxymethyl)-/ , /
.

Da, da,! -Pentamethyl-/, 3゜q-tetrahydronaphthalene ([α]$4@-23,zaO(0/,benzene)) J, 00 g (7,4 dmmol) f
, 30d dissolved in benzene, lead tetraacetate @, oo g
(De, OJ mmo)) Anhydrous salt (shiritium〇, 10
g (/7.9 mmoj) f was added, and the mixture was heated under reflux for 4 hours. After washing the reaction solution with water and then with diluted hydrochloric acid, unreacted carboxylic acid was removed with ≦thiammonia water. benzene layer t
After drying and concentration, it was purified by column chromatography to give (→-3-(chloromethyl)-/, /, 4', tI, 7-pentamethyl-/).

Ko,,! , Q-tetrahydronaphthalene was obtained. 0.3 from the ammonia aqueous layer. ! r g (/, j4<mmoj
) was recovered. The amount of collected carboxylic acid was 77% per consumed carboxylic acid.

[α] 54g + “t-/’ (C/t!1
-hexane) NMR (0CiJ4) δ (ppm) =
/, 01 (JHI), to C3HT8>, 83a (
, ya, g), he J de (JH, m), 8 ltr ~/J
j(,?H,m), J, JJ(lH,t), 3. tt(
lH, aa), t, tt ~7. xz (, ya, m
)(s) -,7-(carboxymethyl) 't
'sda, *, 1-pentamethyl-1,co, 3゜dirtytrahydronaphthalene ([α]5460koy, z0(C/
, benzene)) in the same manner as in Example 1 (1) (6) -3-(riqromethyl)-/, /, 4t
, ll, t-pentamethyl-7,co, 3. Dilutetrahydronaphthalene was obtained.

The NMR spectrum of [α]546-co6-JO (0/T n "x xane) was the same as that of Example (1).

(3) Lithium aluminum hydride in nitrogen, jJg(
0,,2! Suspend in J mrno fTH170d■
)-3 (chloromethyl) /*/+da, da.

6-pentamethyl-/, 2,3. II-Tetrahydronaphthalene ([α]+st, 10(0/.

nA xane)) 12. yg(0,2!;/mrno
Then, a solution of 100 ml of rHIF was added dropwise. After heating and refluxing for a waiting time, the reaction solution was treated with aqueous THF in nitrogen, and then diluted hydrochloric acid≦00d was added, followed by extraction with n-hexane.

After washing the extract with saturated saline, drying, concentrating, and distilling the eA
, Og (0,2/3, frnol, I 4%)
(8)-/.

l, 3. Da, Hiroshi, t-hexamethyl-/.

Tip 3. Dilutenaphthalene was obtained.

(α) s4. −&? , 10 (C/, rioa*rum)
bpO-5=? /'C m(cca4)δ(ppm)-0-94(Qd),/,
θJ (JIi, s), /, 2/(JH, m), /,
,24t(3H,s),/,J-ruI),/,ki~i
, t6 (class, m) 1, Z 23'(J'H,s ), l
-7/ ~7. /4' (3H, m) (9) (6)
-3-(chloromethyl)-/, /, 9゜q, 6-bentamethyl-/, 2,3. Tertetrahydronaphthalene (
[α]54g -,;%,,20(C/,!1-hexane)) was carried out in the same manner as in Example-(3), and (6
)-/, /, 3゜da, g, 6-hexamethyl-/, λ,
3° Cutetrahydronaphthalene was obtained.

[α]546 + What? ' (C/, chlorophor A)
bpO-'=? /"C' (branch) During autoclaving, (8)-J-(lyalomethyl)-/, /, Q, 4t, 6-bentamethyl-/,
2, 3. II-Tetrahydronaphthalene X) 0119
(0.7 g rmthlA) inpropatol solution (/θd), sodium acetate,
Insert field a), /θ chip pd -C/6θ cape, r OKf
A hydrogen pressure of /an'' was applied and the mixture was stirred at jθ゛C for 72 hours.

After cooling, the pd-C was separated from P and extracted with hexane without adding water. After washing with saturated sodium bicarbonate solution, drying and concentrating, 772 g9 (θ, 796 mnol) of (S)-/
,/,3. 4t, 6-hexamethyl-/, 2
, 3.11-tetrahydronaphthalene was obtained.

(6) Hydrogenation uP uA gsxy in nitrogen JE
<o, sumad), lithium aluminum hydride 7
8g7F (θ'e 04K nag ) was suspended in THF, (S)-3-(chloromethyl) -/, /,
tIt, 4t.

7-pentamethyl-/, 2,3. lI-tetrahydronaphthalene 94t, l, 2F (0,37 mo-g
) was added dropwise, and the mixture was heated under reflux for 36 hours. The reaction solution was treated with dilute hydrochloric acid and extracted with n-hexane. After washing with saturated saline, drying, concentrating, and distilling.
(0,-776mJ) of (S)-/, /, 3. Gu, 4
t, O-hexamethyl-/, 2,3. 'I-tetrahydro t7talene was obtained.

Example 3 Optical activity 7-7 cetyl/, /, 3. lI.

Dow 6-hexamethyl-/, λ, 3. Method for producing cootetrahydronaphthalene (1) (8) -/, /, 3. da, q, 6-hexamethyl-/, 2. "%, 4-tetrahydronaphthalene ([α)546'19.IQ (C/, ys-hexane)) 100.OF (0,4t63
moJ) in 9θ10/, 2-dichloroethane,
x, of (0, how many grams mo-& ) of acetyl chloride and 7/
, 0 (0, JJ3 mcJ) of anhydrous aluminum chloride was added, and the mixture was stirred at 20°C for 7 hours. 300% reaction solution
After treatment with 70% hydrochloric acid (1), the layers were separated.

The organic layer was washed with dilute hydrochloric acid and then with a saturated sodium carbonate aqueous solution, dried, concentrated, and distilled to yield /(1), JP (θ, da/7
meJ, (8) -7-acetyl-/,
/, 3.4t, da, 6-heki! methyl/, ko, 3,4
t-tetrahydronaf-talene was obtained.

bpo・2-762°C [α)546 -36. 0 (C/, ethanol) NM
R(Cce,)δ(ppm) = 0. yza (Ja,
a ), /, 0A(JH,m), /, ,26(
JH,m),/,3θ(61(,s),/,'I0
-/, 17 (JH,tn), -2,'l! (J
H, a) 1.2. '19 (JH,s), 7. θ
4(/H,s), 7. jQ(/H,s) ri)−
/, /, 3. l/l, ri, otsu-hexamethyl-/, 2
,3. 'l-Tetrahydronaphthalene ([α]546+
The procedure was carried out in the same manner as (6)-6-7 cetyl/, /, 2 in Example 3 using
．． G, Q, 7-hexamethyl-/, 2,3. 'l-Tetrahydronaphthalene was obtained.

bpO・2 = /θ de °C [α)546 +31b, 20 (C/ , ethanol) Patent applicant Sumitomo Chemical Co., Ltd. Procedural amendment (voluntary) Commissioner of the Patent Office Shima 1) Haruki Tono1, Indication of the case 1986 Patent Application No. 107881 2, Title of the invention: Optically active tetrahyto-lonaphthalene derivatives and their manufacturing process 3, Relationship with the person making the amendment Case Address of patent applicant: 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative: Takeshi Kamigata 4, Address: 5-15-5 Kitahama, Higashi-ku, Osaka, Detailed description of the invention in the specification subject to amendment.

6. Contents of amendment 1) r(0,252mn) on page 27, line 10 of the specification
+ol)J is corrected to r(0,252mol)J.

2) Line 14 (7) r (0,251 mmol
)J is corrected to r (0,251 mol)J.

that's all

Claims (1)

[Claims] (1) An optically active tetrahydronaphthalene derivative represented by formula (I*). (In the formula, R represents an alkyl group.) (To) An optically active tetralin-conductor represented by the formula (l*) is decarboxylated to obtain an optically active tetrahyl I# lonaphthalene derivative represented by the formula (tX), The optically active tetra-F-cross t7 talene derivative OII method is characterized in that this is then acetylated. (In the formula, K represents an alkyl group.) (In the formula, Rti represents a furkyl group.) (In the formula, R represents the same meaning as above.) U) Optically active d(2-methyl-propenyl) -S,S-dimethyltetrahydro-λ-7lanone (commonly known as paisine) and alkyl-substituted benzene are reacted in the presence of a Friedelkraff catalyst, or I<irosine and alkyl-substituted benzene are reacted with an acid catalyst. After that, it is treated in the presence of Friedelkraft's tentacles O to obtain an optically active tetraV derivative represented by the formula (l*), and then deacidized to obtain the formula "
1? ) is obtained by obtaining an optically active tetrahydronaphthalene derivative represented by formula (1) and acetylating it.
(In the formula, R represents an alkyl group.) (In the formula, R represents an alkyl group.) (In the formula, R has the same meaning as above. 0)