JP2000191559A - Standard of 1-phenyl-4-(1-phenylethyl)tetralin for styrene oligomer analysis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain new compounds of 1-phenyl-4-(1-phenylethyl)tetralins useful as a standard for the analysis of styrene oligomers which are formed in an extremely small amount during a styrene polymerization reaction. SOLUTION: 1S*-Phenyl-4S*-(1R*-phenylethyl)tetralin of formula I. As preferable standard, compounds of formula II to IV are further cited. These compounds are obtained by treating a compound of formula V for 1-10 hr by catalytic hydrogenation in the presence of a catalyst, and subsequently separating and purifying the steric isomers of the obtained product by a high-speed liquid chromatography or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a simple method for producing 1-phenyl-4- (1-phenylethyl) tetralin, which can be obtained in a very small amount in the production of polystyrene, and a qualitative analysis of styrene oligomer contained in polystyrene. 1S ^* -phenyl-4S ^* -useful as a standard for analysis such as quantification
(1R ^* -phenylethyl) tetralin, 1S ^* -phenyl-4R ^* -(1S ^* -phenylethyl) tetralin, 1
The present invention relates to S ^* -phenyl-4S ^* -(1S ^* -phenylethyl) tetralin, 1S ^* -phenyl-4R ^* -(1R ^* -phenylethyl) tetralin and a method for producing the same.

[0002]

2. Description of the Related Art Polystyrene is a polymer obtained by polymerizing styrene, and is widely used for food containers and the like. A small amount of styrene oligomer remains in polystyrene, and its content is determined by a method for producing polystyrene,
Or there is variation depending on the type.

Kawamura et al. Have identified styrene oligomers contained in general-purpose polystyrene, which is a homopolymer of styrene, and determined or estimated the structures of several styrene dimers and styrene trimers [Food Hygiene Science] Magazine, Vol. 39, No. 2, p. 110 (1998)]. In this report, 1-phenyl-4- (1-phenylethyl) tetralin is described, but its steric structure remains unknown.

A method for producing 1-phenyl-4- (1-phenylethyl) tetralin is disclosed in Japanese Unexamined Patent Publication No. Hei.
11070], which are fractionated by distillation under reduced pressure from the styrene oligomer obtained during the production of polystyrene, and the resulting 1-phenyl-4- (1-phenylethyl) tetralin is also used. There is no description about a trace amount and a stereoisomer.

[0005]

The present invention is directed to cyclic styrene trimers for which an effective production method has not been established.
It is an object of the present invention to provide 1-phenyl-4- (1-phenylethyl) tetralin by a synthetic method that is simple and can be mass-produced.

[0006] Further, the stereoisomers completely unknown to date have been separated and purified to clarify the absolute configuration of each stereoisomer when a phenyl group having a tetralin ring bonded to the β side is assumed. Thus, a highly pure 1-phenyl-4- (1-phenylethyl) tetralin useful in the analysis of styrene oligomers, namely, 1
S ^* -phenyl-4S ^* -(1R ^* -phenylethyl) tetralin, 1S ^* -phenyl-4R ^* -(1S ^* -phenylethyl) tetralin, 1S ^* -phenyl-4S ^* -(1
S ^* -phenylethyl) tetralin, 1S ^* -phenyl-
It is intended to provide 4R ^* -(1R ^* -phenylethyl) tetralin.

[0007]

SUMMARY OF THE INVENTION The present invention provides the following items 1 to 7. Item 1. General formula (I)

[0008]

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A compound represented by the formula: Item 2. General formula (II)

[0010]

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A compound represented by the formula: Item 3. General formula (III)

[0012]

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A compound represented by the formula: Item 4. General formula (IV)

[0014]

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A compound represented by the formula: Item 5. Item 7. An analytical standard comprising the compound according to any one of Items 1 to 4. Item 6. A method for producing a compound represented by the general formula (VI), comprising reducing the compound represented by the general formula (V):

[0016]

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Item 7. Items 1 to 4, wherein stereoisomers of the compound of the general formula (VI) obtained in Item 6 are separated.
A method for producing a compound according to any one of the above.

[0018]

DETAILED DESCRIPTION OF THE INVENTION 1-phenyl-4 in the present invention
-(1-Phenylethyl) tetralin can be produced according to the following <Reaction Scheme 1>. <Reaction process formula 1>

[0019]

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(Step A) First, 1 mol of benzyl phenyl ketone (1) is reacted with 1 to 2 mol of cinnamyl bromide (2) under basic conditions at 0 ° C. to room temperature for 1 to 24 hours. The compound represented by 3) can be obtained.

As the benzyl phenyl ketone and cinnamyl bromide used in the present process, commercially available products can be used.

The base mentioned here includes sodium hydride and the like.

This reaction is usually performed in a solvent, and examples of the solvent include dimethylformamide, dimethylsulfoxide and the like. (Step B) Next, the compound of the formula (3) is added in the presence of an acid catalyst.
The compound represented by the formula (4) can be obtained by reacting at about 80 ° C. to 200 ° C. or at a temperature at which the solvent is refluxed for 1 to 60 hours.

The stereoisomer of the compound represented by the formula (4) can be separated and purified by using silica gel chromatography or the like.

In this reaction formula, examples of the acid catalyst include p-toluenesulfonic acid.

This reaction can be carried out without a solvent or in a solvent such as benzene, toluene, xylene or mesitylene. (Step C) Subsequently, 1 to 2 mol of a reagent which generates a methyl anion in 1 mol of the compound of the formula (4) is added at room temperature to 10 mol.
The compound represented by the formula (5) can be obtained by reacting at 0 ° C. to a temperature at which the solvent is refluxed for 1 to 24 hours.

The stereoisomer of the compound represented by the formula (5) can be separated and purified by using silica gel chromatography, high performance liquid chromatography and the like.

In the present reaction, examples of the compound that generates a methyl anion include Grignard reagents such as methylmagnesium bromide, and organometallic compounds such as methyllithium.

This reaction is usually performed in a solvent, and examples of the solvent include diethyl ether, tetrahydrofuran, diisopropyl ether and the like. (Step D) Next, 1 mol of the compound of the formula (5) is reacted with 1 to 2 mol of a dehydrating reagent at room temperature to about 100 ° C. or at a temperature at which the solvent is refluxed for 1 to 5 hours, whereby The compounds represented can be obtained.

The compound represented by the formula (V) obtained in this reaction formula includes those in which the dehydration reaction has progressed to an exomethylene type, one in which the dehydration reaction has progressed to a tetrasubstituted type, Each isomer of isomerized to, and
Refers to all of these stereoisomers. These can be separated and purified by using silica gel chromatography, high performance liquid chromatography and the like.

In the present reaction, examples of the dehydrating reagent include methanesulfonyl chloride, p-toluenesulfonyl chloride, trifluoroacetic anhydride, and thionyl chloride.

This reaction can be carried out without solvent or in a solvent such as chloroform or dichloromethane. (Step E) Finally, the compound of the formula (VI) can be obtained by subjecting the compound of the formula (V) to a catalytic hydrogenation reaction at room temperature for 1 to 10 hours in the presence of a catalyst.

The stereoisomer of the compound of the present invention represented by the formula (VI) can be separated and purified by using high performance liquid chromatography or the like.

In this reaction, the compounds of formulas (I), (II), (III),
The compounds of the present invention represented by (IV) each have 1S^*-Phenyl
-4S^*-(1R^*-Phenylethyl) tetralin, 1S
^*-Phenyl-4R^*-(1S^*-Phenylethyl) tet
Laline, 1S^*-Phenyl-4S^*-(1S^*-Phenyl
Ethyl) tetralin, 1S^*-Phenyl-4R^*-(1R
^*-Phenylethyl) tetralin.

The catalyst in this reaction includes palladium-activated carbon and the like.

This reaction is usually performed in a solvent, and examples of the solvent include ethyl acetate, methanol, ethanol, acetic acid and the like.

In order to determine the absolute configuration of the present compound assuming that the phenyl group having a tetralin ring bonded to the β side, 1S ^* − was determined by a production method comprising the following <Reaction Scheme 2>. Phenyl-4S ^* -(1S ^* -phenylethyl) tetralin and 1S ^* -phenyl-4R ^* -
(1R ^* -phenylethyl) was prepared. <Reaction process formula 2>

[0038]

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(Step F) The compound represented by the formula (VA) separated and purified from the compound represented by the formula (V) obtained above is subjected to a catalytic hydrogenation reaction at room temperature in the presence of a catalyst at room temperature. ~ 1
A mixture of the compounds of the present invention represented by the formulas (III) and (IV) can be obtained by performing the reaction for 0 hours.

The mixture of the stereoisomers of the compound of the present invention represented by the formula (III) and the formula (IV) can be separated and purified by using high performance liquid chromatography or the like.

The catalyst in this reaction includes palladium-activated carbon and the like.

This reaction is usually performed in a solvent, and examples of the solvent include ethyl acetate, methanol, ethanol, acetic acid and the like.

The inventor has set forth the above <reaction process formula 1> and
By comparing the physical properties of the compound obtained in <Reaction Scheme 2>, the absolute configuration of the present compound was clarified when the phenyl group to which the tetralin ring was bonded was assumed to be on the β side. The relationship between the structure of the present compound and the retention times of gas chromatography and high performance liquid chromatography is as follows ^: 1S ^* -phenyl-4S ^* -(1R ^* -
Phenylethyl) tetralin, 1S ^* -phenyl-4R ^*
-(1S ^* -phenylethyl) tetralin, 1S ^* -phenyl-4S ^* -(1S ^* -phenylethyl) tetralin,
1S ^* -phenyl-4R ^* -(1R ^* -phenylethyl)
Tetralin. Analysis conditions (gas chromatography) Column: DB-WAX (0.25 mmid × 30)
m, df = 0.25 μm) Column temperature: 100 ° C. → 20 ° C./min. → 250 ° C
(30 min.) Inlet temperature: 250 ° C Detector temperature: 250 ° C Carrier gas: He (1.3 ml / min.) Analysis conditions (high-performance liquid chromatography) Column: TSKgel ODS-80TSQA (4.6)
mm × 250 mm) Column temperature: 50 ° C. Mobile phase: 85% methanol, 15% water Flow rate: 1.5 ml / min. Detection wavelength: 254 nm

[0044]

Next, the present invention will be described in more detail with reference to production examples. Production Example 1) 1S ^* -benzoyl-4S ^* -phenyltetralin, 1R ^* -benzoyl-4S ^* -phenyltetralin Sodium hydride (12.2 g, 1.2 eq.) Was n-
After washing with hexane, N, N-dimethylformamide (250 ml) was added to form a suspension. This was stirred under cooling to 0 ° C., and cinnamyl bromide (37.9 ml,
1.3 eq. ) Was added dropwise. After the hydrogen bubbling is finished,
The mixture was further stirred at room temperature for 30 minutes. To this, benzylphenyl ketone (50.0 g, 0.25 mol) dissolved in N, N-dimethylformamide (50 ml) was added dropwise,
Stirred at room temperature for 1 hour. Ice water was added to the reaction solution to stop the reaction, followed by extraction with toluene and washing with saturated saline.
The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
1,2,5-Triphenyl-4-penten-1-one was obtained as a crude product.

The crude product of 1,2,5-triphenyl-4-penten-1-one previously obtained, toluene (1000 m
l) Add P-toluenesulfonic acid (71.0 g, 1.
5 eq. ) And silica gel (100.0 g)
Heated to reflux overnight. After the precipitate was separated by filtration, the solvent was concentrated under reduced pressure by about 80%, and the residual organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and a saturated saline solution. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography (n-hexane: ethyl acetate = 9: 1) to obtain a crude product of 1-benzoyl-4-phenyltetralin as a yellow oil. 72.9 g of material were obtained. This is n
Crystallization was performed with a mixed solvent of -hexane / diethyl ether to obtain 48.8 g (62.5%) of 1-benzoyl-4-phenyltetralin as a white powder.

The 1-benzoyl-4-phenyltetralin was further subjected to silica gel chromatography (n-hexane: toluene: ethyl acetate = 25: 25: 1) to give 1S ^* -benzoyl-4S ^* -phenyltetralin as white powder and It was separated into white powder 1R ^* -benzoyl-4S ^* -phenyltetralin. 1S ^* -benzoyl-4S ^* -phenyltetralin ¹ H-NMR (CDCl ₃ ) δ: 8.03 (d, 2H, J = 7.3 Hz, Ar-
H), 7.59 (dd, 2H, J = 7.3, 7.3H)
z, Ar-H), 7.50 (dd, 2H, J = 7.3,
7.8 Hz, Ar-H), 7.31-7.20 (m, 3
H, Ar-H), 7.12-7.05 (m, 4H, Ar
-H), 6.99-6.96 (m, 1H, Ar-H),
6.94-6.92 (m, 1H, Ar-H), 4.97
(Dd, 1H, J = 6.3, 6.3 Hz, 1-CH),
4.26 (dd, 1H, J = 5.8, 6.3 Hz, 4-
CH), 2.32-2.23 (m, 2H), 2.06-
2.00 (m, 1H), 1.94-1.86 (m, 1
H) ¹³ C-NMR (CDCl ₃ ) δ: 202.0, 146.6, 139.7, 136.
4, 135.1, 132.9, 130.3, 129.
0,128.7 × 2,128.6 × 4,128.2 ×
2,126.7, 126.2, 126.0, 47.5,
45.2, 30.4, 25.1 Mass EI method: 312 (M ⁺ ) Melting point: 104 to 106 ° C. Elemental analysis: As C ₂₃ H ₂₀ O Theoretical value (%): C: 88.42, H: 6. 46, O:
5.12 Observed value (%): C: 88.41, H: 6.56, O:
5.03 1R ^* -benzoyl-4S ^* -phenyltetralin ¹ H-NMR (CDCl ₃ ) δ: 8.08 (d, 2H, J = 7.3 Hz, Ar-
H), 7.63-7.59 (m, 1H, Ar-H),
7.52 (dd, 2H, J = 7.3, 7.8 Hz, Ar
-H), 7.33-7.19 (m, 5H, Ar-H),
7.13-7.09 (m, 2H, Ar-H), 6.99
-6.97 (m, 1H, Ar-H), 6.93-6.9
1 (m, 1H, Ar-H), 4.96 (dd, 1H, J
= 5.9, 5.9 Hz, 1-CH), 4.13 (dd,
1H, J = 5.9, 7.8 Hz, 4-CH), 2.19
−2.15 (m, 2H), 2.15 to 2.08 (m, 1
H), 2.03-1.98 (m, 1H ) 13 C-NMR (CDCl 3) δ: 201.9,146.7,140.4,136.
4, 135.0, 132.9, 130.2, 129.
2,128.9 × 2,128.6 × 2,128.5 ×
2,128.2 × 2,126.7,126.0 × 2,4
7.0, 45.5, 29.9, 25.6 Mass EI method: 312 (M ⁺ ) Melting point 101-103 ° C. Elemental analysis: As C ₂₃ H ₂₀ O Theoretical value (%): C: 88.42, H: 6.46, O:
5.12 Observed value (%): C: 88.44, H: 6.58, O:
4.98 Production Example 2) 1S ^* -Phenyl-4R ^* -(1-phenylethenyl) tetralin, 1-E- (α-methylbenzylidene) -4-phenyltetralin 1S ^* -benzoyl-4S ^* -phenyltetralin ( 4
5.0 g, 0.14 mol) of diethyl ether (60
0 ml) solution was stirred at room temperature, and a 3.0 M methylmagnesium bromide diethyl ether solution (62.1 m
1, 1.3 eq. ) Was added dropwise. After heating under reflux for 1 hour, the reaction solution was cooled to 0 ° C., and a 4N aqueous hydrochloric acid solution was added dropwise thereto to stop the reaction. The organic layer was extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. After concentration under reduced pressure, 1- (1-hydroxy-1-phenylmethyl) -4-phenyltetralin was obtained as a crude product.

The 1- (1-hydroxy-1-fe) previously obtained
Nylmethyl) -4-phenyltetralin
Methanesulfonyl chloride in roloform (50 ml) solution
(22.0 ml, 2 eq.) And heat for 3 hours
Shed. Neutralized with 4N aqueous sodium hydroxide in an ice bath
After that, the mixture was extracted with ethyl acetate and washed with saturated saline.
Was. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
After that, silica gel chromatography (n-hexane)
Sun: toluene = 15: 1-10: 1)
S^*-Phenyl-4R^*-(1-phenylethenyl) tet
41.5 g (93.4%) of larin was obtained as a white powder.
Was. Also, 1-E- (α-methylbenzylidene) -4-
861 mg of phenyltetralin as a white powder (1.
9%). 1S^*-Phenyl-4R^*-(1-phenylethenyl) te
Tralin¹ H-NMR (CDCl_Three) Δ: 7.38-7.05 (m, 13H, Ar-H),
6.90 (d, 2H, J = 7.8 Hz, Ar-H),
5.43 (s, 1H, 2'-CH), 4.76 (s, 1
H, 2'-CH), 4.23-4.16 (m, 1H + 1)
H, 1-CH, 4-CH), 2.27-1.22 (m,
1H), 2.05-1.93 (m, 1H), 1.81-
1.71 (m, 1H), 1.69-1.60 (m, 1
H)¹³ C-NMR (CDCl_Three) Δ: 152.8, 147.1, 141.3, 139.
3,138.7,129.9,129.5,128.4
× 2, 127.9 × 2, 127.8 × 2, 127.0,
126.4 × 2, 125.8, 125.7, 125.
6,116.0,45.1,44.8,29.7,2
5.5 Mass EI method: 310 (M⁺) Melting point 72-74 ° C Elemental analysis: C_{twenty four}H_{twenty two}Theoretical value (%): C: 92.85, H: 7.15 Actual value (%): C: 92.69, H: 7.19 1-E- (α-methylbenzylidene) -4-phenylte
Tralin¹ H-NMR (CDCl_Three) Δ: 7.50 (d, 2H, J = 7.8 Hz, Ar−
H), 7.35-7.10 (m, 10H, Ar-H),
6.88 (d, 2H, J = 7.3 Hz, Ar-H),
4.03-3.99 (m, 1H, 4-CH), 2.45
-2.38 (m, 1H), 2.32-2.27 (m, 1
H), 2.26 (s, 3H, CH_Three), 2.15-2.
06 (m, 1H), 1.90-1.81 (m, 1H)¹³ C-NMR (CDCl_Three) Δ: 145.5, 144.9, 142.0, 137.
6,132.6,132.4,128.8,128.4
× 3,128.1 × 6,126.5,126.1,12
5.9, 125.0, 46.0, 33.1, 99.0,
23.5 Mass EI method: 310 (M⁺) Melting point 122-125 ° C Elemental analysis: C_{twenty four}H_{twenty two}Theoretical value (%): C: 92.85, H: 7.15 Actual value (%): C: 92.87, H: 7.201 IR^*-Benzoyl-4S^*-Departing from phenyltetralin
Using the starting materials, the following compounds were produced in the same manner as in Production Example 2.
did. Production Example 3) 1S^*-Phenyl-4S^*-(1-phenyl
Ethenyl) tetralin¹ H-NMR (CDCl_Three) Δ: 7.44 (d, 2H, J = 6.8 Hz, Ar−
H), 7.36-7.07 (m, 11H, Ar-H),
6.88 (d, 2H, J = 7.8 Hz, Ar-H),
5.46 (s, 1H, 2'-CH), 4.73 (s, 1
H, 2'-CH), 4.23-4.17 (m, 1H),
4.05 (dd, 1H, J = 7.3, 7.8 Hz),
1.95-1.85 (m, 3H), 1.79-1.77
(M, 1H)¹³ C-NMR (CDCl_Three) Δ: 153.7, 147.0, 141.6, 140.
1, 138.2, 130.1, 129.8, 128.4
× 2, 128.0 × 2, 127.9 × 2, 127.0,
126.4 × 2, 126.0, 125.7, 125.
6,116.8,46.2,44.2,29.1,2
6.1 Mass EI method: 310 (M⁺) Melting point 47-53 ° C Elemental analysis: C_{twenty four}H_{twenty two}Theoretical value (%): C: 92.85, H: 7.15 Actual value (%): C: 92.90, H: 7.16 Production Example 4) 1S^*-Phenyl-4R^*-(1S^*-Pheni
Ruethyl) tetralin, 1S^*-Phenyl-4R^*-(1
R^*-Phenylethyl) tetralin 1S^*-Phenyl-4R^*-(1-phenylethenyl) te
Tralin (41.0 g, 0.13 mol) was added to ethyl acetate
(200 ml), and 10% Pd / C (4.
1g) and vigorously stirred at room temperature under a hydrogen atmosphere for 7 hours.
did. After filtration through celite (ethyl acetate), the mother liquor was concentrated under reduced pressure.
And the resulting crude product is chromatographed on silica gel.
(n-hexane: diethyl ether = 30: 1)
And 1S ^*-Phenyl-4R^*-(1-phenylethyl)
39.0 g (94.8 g) of tetralin as a colorless oily substance
%)Obtained.

The 1S ^* -phenyl-4R ^* -(1-phenylethyl) tetralin was further subjected to high performance liquid chromatography (TSKgel ODS-80TSQA, 90% methanol-10% water) to give 1S ^* -phenyl- as a white powder.
It was separated into 4R ^* -(1S ^* -phenylethyl) tetralin and white powder 1S ^* -phenyl-4R ^* -(1R ^* -phenylethyl) tetralin. 1S ^* -phenyl-4R ^* -(1S ^* -phenylethyl)
Tetralin ¹ H-NMR (CDCl ₃ ) δ: 7.33 (d, 2H, J = 7.8 Hz, Ar-
H), 7.25-7.10 (m, 9H, Ar-H),
7.06-7.03 (m, 1H, Ar-H), 6.95
-6.93 (m, 2H, Ar-H), 6.77 (d, 1
H, J = 7.8 Hz, Ar-H), 3.90 (dd, 1
H, J = 5.9, 5.9 Hz, 1-CH), 3.17−
3.12 (m, 1H + 1H, 4-CH, 1'-CH),
2.15 to 2.07 (m, 1H, 2ax.-CH),
1.85-1.75 (m, 1H, 3ax.-CH),
1.65-1.58 (m, 1H, 2 eq. -CH),
1.51-1.42 (m, 1H, 3 eq. -CH),
1.32 (d, 3H, J = 6.8 Hz, CH ₃ ) ¹³ C-NMR (CDCl ₃ ) δ: 147.6, 145.3, 139.9, 139.
7,129.9 × 2,128.5 × 2,128.0 ×
4,127.6 × 2,125.8 × 2,125.6,1
25.1, 44.4, 44.3, 44.2, 28.9,
22.0, 20.9 Mass CI method: 313 (M + H) ⁺ melting point 56-57 ° C Elemental analysis: as C ₂₄ H ₂₄ Theoretical value (%): C: 92.26, H: 7.74 Actual value (%) ): C: 91.98, H: 7.97 1S ^* -phenyl-4R ^* -(1R ^* -phenylethyl)
Tetralin ¹ H-NMR (CDCl ₃ ) δ: 7.34-7.16 (m, 9H, Ar-H), 7.
12-7.06 (m, 3H, Ar-H), 7.01-
6.98 (m, 1H, Ar-H), 6.75 (d, 1
H, J = 7.8 Hz, Ar-H), 4.01 (dd, 1
H, J = 5.8, 8.3 Hz, 1-CH), 3.58
(Dq, 1H, J = 6.8, 7.3 Hz, 1′-C
H), 3.27 (brq, 1H, J = 6.8 Hz, 4-
CH), 2.18-2.09 (m, 1H, 2ax.-
H), 1.78-1.65 (m, 1H + 1H, 2 eq.
-CH, 3ax. -CH), 1.63-1.55 (m,
1H, 3eq. -CH), 1.15 (d, 3H, J =
7.3 Hz, CH ₃ ) ¹³ C-NMR (CDCl ₃ ) δ: 147.1, 145.3, 140.8, 139.
4,129.6,128.6 × 2,128.2 × 2,1
28.0 × 2, 127.9 × 2, 127.3, 125.
9, 125.8, 125.6, 125.3, 46.6
44.7, 42.8, 31.8, 22.2, 13.8 Mass CI method: 313 (M + H) ⁺ melting point 92-94 ° C Elemental analysis: As C ₂₄ H ₂₂ Theoretical value (%): C: 92 .26, H: 7.74 Actual value (%): C: 92.01, H: 7.81 1S ^* -phenyl-4S ^* -(1-phenylethenyl) tetralin was used as a starting material, Production Example 4 The following compounds were produced in the same manner as described above. Production Example 5) 1S ^* -phenyl-4S ^* -(1R ^* -phenylethyl) tetralin, 1S ^* -phenyl-4S ^* -(1
S ^* -phenylethyl) tetralin 1S ^* -phenyl-4S ^* -(1R ^* -phenylethyl)
Tetralin ¹ H-NMR (CDCl ₃ ) δ: 7.36 (d, 2H, J = 7.3 Hz, Ar-
H), 7.27-7.16 (m, 9H, Ar-H),
7.09-7.05 (m, 1H, Ar-H), 6.97
−6.95 (m, 2H, Ar-H), 6.84 (d, 2
H, J = 7.8 Hz, Ar-H), 4.01 (dd, 1
H, J = 7.3, 8.8 Hz, 1-CH), 3.20
(Dq, 1H, J = 7.3, 7.3 Hz, 1′-C
H), 3.02-2.98 (m, 1H, 4-CH),
_{1.95-1.79 (m, 2H, 2-} CH 2), 1.7
9-1.67 (m, 1H, 3ax.-CH), 1.66
-1.58 (m, 1H, 3 eq. -CH), 1.38
(D, 3H, J = 7.3 Hz, CH ₃ ) ¹³ C-NMR (CDCl ₃ ) δ: 147.6, 145.4, 139.7, 139.
6,130.4,130.3,128.5 × 2,12
8.2 × 2,128.1 × 2,127.6 × 2,12
6.0, 125.9, 125.7, 124.9, 46.
2,44.6,44.3,29.6,24.4,21.
2 Mass CI method: 313 (M + H) ⁺ melting point 104-106 ° C Elemental analysis: as C ₂₄ H ₂₄ Theoretical value (%): C: 92.26, H: 7.74 Actual value (%): C: 92. 04, H: 7.99 1S ^* -phenyl-4S ^* -(1S ^* -phenylethyl)
Tetralin ¹ H-NMR (CDCl ₃ ) δ: 7.31-7.18 (m, 8H, Ar-H), 7.
11-7.09 (m, 2H, Ar-H), 7.05-
6.97 (m, 3H, Ar-H), 6.92-6.90
(M, 1H, Ar-H), 4.15 (dd, 1H, J =
6.3, 6.3 Hz, 1-CH), 3.48 (dq, 1
H, J = 6.8, 6.8 Hz, 1'-CH), 3.06
(Brq, 1H, J = 6.8 Hz, 4-CH), 2.1
_{0-1.99 (m, 2H, 2-} CH 2), 1.87-
1.76 (m, 1H, 3ax. -CH), 1.49-
1.38 (m, 1H, 3 eq. -CH), 1.24
(D, 3H, J = 6.8 Hz, CH ₃ ) ¹³ C-NMR (CDCl ₃ ) δ: 147.4, 145.6, 139.9, 139.
1,130.4,128.7 × 2,128.2,12
8.0 × 4, 127.9 × 2, 125.8, 125.
7, 125.6, 125.5, 45.6, 45.0, 4
3.3, 30.2, 21.1, 15.5 Mass CI method: 313 (M + H) ⁺ melting point 119-122 ° C Elemental analysis: as C ₂₄ H ₂₄ Theoretical value (%): C: 92.26, H : 7.74 Actual value (%): C: 92.01, H: 7.88 Production Example 6) 1S ^* -phenyl-4S ^* -(1S ^* -phenylethyl) tetralin, 1S ^* -phenyl-4R ^* - (1
R ^* -phenylethyl) tetralin 1-E- (α-methylbenzylidene) -4-phenyltetralin (250 mg, 0.81 mmol) was dissolved in ethyl acetate (2.5 ml), and 10% Pd / C (2
5 mg) and stirred vigorously at room temperature under a hydrogen atmosphere for 1 hour. After filtration through celite (ethyl acetate), the mother liquor was concentrated under reduced pressure, and the obtained crude product was purified by silica gel chromatography (n-hexane: diethyl ether = 30: 1) to give 1S ^* -phenyl-4S ^* -. (1S ^* -phenylethyl) tetralin and 1S ^* -phenyl-4R ^* -(1R ^*
247 mg (98.1%) of a mixture of -phenylethyl) tetralin as a colorless oil.

The mixture was further subjected to high performance liquid chromatography (TSKgel ODS-80TSQA, 90%
Separation into white powder 1S ^* -phenyl-4S ^* -(1S ^* -phenylethyl) tetralin and white powder 1S ^* -phenyl-4R ^* -(1R ^* -phenylethyl) tetralin with methanol-10% water). did.

[0050]

The compounds of the present invention are of high purity, and the absolute configuration of each compound is determined when the phenyl group bonded to the tetralin ring is assumed to be on the β side. It is useful as an analytical standard such as qualitative and quantitative analysis.

Continued on the front page (72) Inventor Toshihiro Yamada 4-1-1, Nishinakajima, Yodogawa-ku, Osaka-shi, Nippon Foods F-term (reference) 4H006 AA01 AA02 AA03 AB81 AC11 AC22 AC24 AC25 AC28 AC83 AD17 BA25 BA61 BB14 BB17 BJ50 FC52 FC56

Claims (7)

[Claims] 1. A compound of the general formula (I) A compound represented by the formula: 2. A compound of the general formula (II) A compound represented by the formula: 3. A compound of the general formula (III) A compound represented by the formula: 4. A compound of the general formula (IV) A compound represented by the formula: (5) An analytical standard comprising the compound according to any one of (1) to (4). 6. A process for producing a compound represented by the general formula (VI), comprising reducing the compound represented by the general formula (V): 7. The method according to claim 1, wherein the stereoisomers of the compound of the formula (VI) obtained in claim 6 are separated.
A method for producing a compound according to any one of the above.