CN1738811A - Preparation method of 1-acetoxy-3-(substituted phenyl)propene compound - Google Patents

Abstract

The compound represented by the formula (I) is obtained by reacting a benzene compound of the formula (IV) or (V) with an alkenylene diacetate of the formula (VI) in the presence of a catalyst containing at least one member selected from the group consisting of (a) a halogenated boron compound, (b) a trifluoromethanesulfonate compound of a group 11 element, (c) a halogen compound of a group 12 element, (d) a trifluoromethanesulfonate compound of tin or an element having an atomic number of 58, 66 to 71, and a halogen compound. R¹，R²H or C₁－C₁₀A ═ corresponds to substituted phenyl of formula (IV) or (V), R³，R⁴＝C₁－C₄M is 0, 1 to 4, n is 1 to 5, and k is 1 or 2.

Description

The preparation method of 1-acetoxy-3-(substituted phenyl)propene compound

technical field

The present invention relates to a preparation method of 1-acetoxy-3-(substituted phenyl)propene compound. In more detail, the present invention relates to a method for preparing a 1-acetoxy-3-(substituted phenyl)propene compound having a phenyl group substituted with an alkoxy group or an alkanedioxy group at the 3-position .

The 1-acetoxy-3-(substituted phenyl)propene compound prepared by the method of the present invention is useful as an intermediate of spices, pharmaceuticals, pesticide products, and other organic synthetic drugs.

Background technique

As a synthetic method of 1-acetoxy-3-(substituted phenyl)propene compound, in Bull, Soc, Chim, France, 1961, P1194-1198, it is disclosed in tetrafluoroethylene activated by boron trifluoride ether coordination compound Synthesis of 1-acetoxy-3-(3,4-dimethoxyphenyl)propene by reacting 1,2-dimethoxybenzene with alkenylene diacetate in the presence of titanium chloride Methods. However, the yield of the target compound obtained by this method is reported to be 62%, which is unsatisfactory. The inventors of the present invention etc., repeated above-mentioned synthetic method, confirmed: the yield of target compound is only 12%, in addition, generate a large amount of by-products, and reaction mixture is brown (comparative example 3 with reference to the present application). In addition, titanium tetrachloride used in this synthesis method is an unstable compound that is decomposed by moisture in the air, and complicated care is required in its handling.

In addition, the present inventors, etc., used the above synthesis method for the reaction of 3,4-methylenedioxybenzene and alkenylene diacetate, due to the titanium tetrachloride activated by the boron trifluoride ether coordination compound , Carry out the decomposition reaction of 3,4-methylenedioxybenzene, the yield of target compound is 43.1%, is unsatisfactory (with reference to the comparative example 1 of this application). Furthermore, in order to suppress or prevent the decomposition of 3,4-methylenedioxybenzene, a reaction was attempted using 0.1 mol of titanium tetrachloride per 1 mol of alkenylene diacetate, but the yield of the target compound decreased. to 9.8% (refer to comparative example 2 of the present application).

In JP-A-55-141437, it is disclosed that in the presence of a stoichiometric amount of Lewis acid, t-butylbenzene, methacrolein and acetyl chloride are reacted to synthesize 1-acetoxy-2-methyl-3- (4-t-Butylphenyl) propene method. In this method, when titanium tetrachloride was used as the Lewis acid, the yield of the target compound was 46.2%, and when boron trifluoride ether complex was used, the yield of the target compound was 2.3%, in either case , the yields of the target compounds are all low, which is unsatisfactory.

Contents of the invention

The object of the present invention is to provide a kind of 1-acetoxy-3-(substituted phenyl)propene compound useful as the intermediate of spices, pharmaceuticals, pesticide products and other organic synthetic drugs with high yield and easy preparation .

The above object can be achieved according to the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention.

The preparation method of the present invention is characterized in that: in order to prepare the 1-acetoxy-3-(substituted phenyl)propene compound represented by the following general formula (I), it contains (a) a boron halide compound, ( b) Trifluoromethanesulfonate compounds of group 11 elements in the periodic table, (c) halogen compounds of group 12 elements in the periodic table, (d) tin or lanthanides with atomic numbers 58, 66-71 In the presence of a catalyst of at least one compound selected from the group consisting of a triflate compound and a halogen compound, one selected from a group of benzene compounds represented by the following general formulas (IV) and (V) Reaction with the alkenylene diacetate compound represented by the following general formula (VI);

(In the above formula (I), R ¹ and R ² each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, wherein R ¹ and R ² can also be mutually Linked to form a cyclic group with the 2-position and 3-position carbon atoms of the propenyl group, and A represents one of the substituted phenyl groups represented by the following formulas (II) and (III),

^R3 and ^R4 each independently represent an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 or 1 to 4, n represents an integer of 1 to 5, and k represents an integer of 1 or 2);

and

(In the above formulas (IV) and (V), R ³ and R ⁴ and n, m and k are as previously described);

(In the above formula (VI), R ¹ and R ² are as described above).

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the benzene compound represented by the above-mentioned general formula (IV) is preferably selected from anisole, o-dimethoxybenzene, p-benzene Choose from diphenol dimethyl ether, phloroglucinol trimethyl ether, and hydroxyhydroquinone trimethyl ether.

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the benzene compound represented by the above general formula (V) is preferably selected from 1,2-methylenedioxybenzene and 1, Choose from 2-ethylenedioxybenzene.

In the preparation method of the 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the alkenylene diacetate represented by the above general formula (VI) is preferably obtained from 3,3-diacetoxy Base-2-methylpropene, 3,3-diacetoxypropene, 3,3-diethoxy-1-methylpropene, 3,3-diacetoxy-2-ethylpropene, 3, Choose from 3-diethoxy-1-ethylpropene and 3,3-diethoxy-1-ethyl-2-methylpropene.

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, in the above-mentioned reaction, the molar ratio of the above-mentioned benzene compound and the above-mentioned alkenylene diacetate compound is preferably used in the range of 1 to 50:1.

In the production method of the 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the amount of the catalyst used is preferably 0.005 to 1 mole relative to 1 mole of the alkenylene diacetate compound. .

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the boron halide compound (a) used in the catalyst is preferably from boron fluoride, boron trifluoride diethyl ether coordination compound , boron trifluoride tetrahydrofuran coordination compound, boron trifluoride acetate complex salt, boron trifluoride dihydrate and boron trifluoride-n-butyl ether coordination compound.

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the trifluoromethanesulfonate compound (b) of Group 11 elements used in the catalyst is preferably from trifluoromethanesulfonic acid Choose between copper and silver triflate.

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the halogen compound (c) of Group 12 elements used in the catalyst is preferably selected from zinc fluoride, zinc chloride, bromide Zinc, zinc iodide, cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, hydrogen fluoride, mercuric chloride, mercuric bromide and mercuric iodide.

In the preparation method of 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the tin used in the catalyst and the trifluoromethanesulfonate The compound and the halogen compound (d) are preferably selected from triflate compounds, fluorides, chlorides, bromides and iodides of tin, cerium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

In the preparation method of 1-acetoxy-3-(substituted phenyl) propene compound of the present invention, above-mentioned reaction is preferably in the compound of above-mentioned general formula (IV), (V) and (VI), above-mentioned catalyst and reaction It is carried out in an atmosphere composed of a gas in which the product does not react.

In the preparation method of the above-mentioned 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the compound of the above-mentioned formula (I) is preferably selected from the compounds represented by the following general formula (VII);

(In the above formula (VII), ^R1 and ^R2 are as described above, and B represents one selected from the group of substituted phenyl groups represented by the following formulas (VIII) and (IX),

In formulas (VIII) and (IX), R ³ , R ⁴ and k are as described above).

The compound represented by the above general formula (VII) is a novel compound.

In the preparation method of the above-mentioned 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the compound of the above-mentioned general formula (I) is preferably from the following formulas (X) and (XI):

and

Select from the represented 1-acetoxy-3-(3,4-C1-C2 alkylenedioxyphenyl)propene. The compounds of the above formulas (X) and (XI) are novel compounds.

In the above-mentioned production method of the 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, in the above-mentioned formula (X) or (XI), it is preferable that R ¹ represents a hydrogen atom, and R ² represents a methyl group.

In the preparation method of the above-mentioned 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, the compound of the above-mentioned general formula (I) is preferably obtained from 1-acetoxy-2-methyl-3-(3 , 4-methylenedioxyphenyl)propene, 1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene, 1-acetoxy-2-methyl Base-3-(4-methoxyphenyl)propene, 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene and 1-acetoxy-2- Choose from methyl-3-(3,4-dimethoxyphenyl)propene. Among these compounds, 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene, 1-acetoxy-2-methyl-3-(3,4 -Ethylenedioxyphenyl)propene, 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene are novel compounds.

The periodic table used in the present invention is based on Group 18 type periodic table, IUPAC, Inorganic Chemical Nomenclature, 1990 rule.

In addition, "trifluoromethanesulfonate" means Tri(fluoro)methanesulphonate.

Detailed ways

The 1-acetoxy-3-(substituted phenyl)propene compound prepared according to the preparation method of the present invention is based on the asymmetric carbon atom and/or double bond contained in the compound represented by the above general formula (I), of course Contains various stereoisomers.

In order to prepare the 1-acetoxy-3-(substituted phenyl) propene compound of the present invention, the method of the present invention comprises: in the presence of the specific catalyst described in detail later, making the compound obtained from the above general formula (IV) and (V) One selected from the group of benzene compounds shown is reacted with the alkenylene diacetate represented by the above general formula (VI). The benzene compound of formula (IV) and (V) corresponds to the substituted phenyl represented by general formula (II) and (III), and the alkenylene diacetate represented by general formula (VI) is in general formula (I) In combination with the A base. Corresponds to 1-acetoxypropenyl.

The specific catalyst used in the process of the present invention contains from

(a) boron halide compound

(b) Trifluoromethanesulfonate compounds of group 11 elements in the periodic table of elements

(c) halogen compounds of elements of group 12 of the periodic table, and

(d) Trifluoromethanesulfonate compounds and halogen compounds of tin and lanthanide elements with atomic numbers 58 and 66-71

At least 1 compound selected from the group formed.

In the method of the present invention, the benzene compound represented by the above general formula (IV) is preferably selected from anisole, o-dimethoxybenzene, hydroquinone dimethyl ether, phloroglucinol trimethyl ether, and hydroxyterequinone Among phenol trimethyl ethers, anisole and o-dimethoxybenzene are particularly preferably used. These can also use a commercial item.

In addition, the benzene compound represented by the general formula (V) is preferably selected from 1,2-methylenedioxybenzene and 1,2-ethylenedioxybenzene.

Furthermore, the alkenylene diacetate represented by the above general formula (VI) is preferably selected from 3,3-diacetoxy-2-methylpropene, 3,3-diacetoxypropene, 3,3 -diethoxy-1-methylpropene, 3,3-diethoxy-2-ethylpropene, 3,3-diethoxy-1-ethylpropene and 3,3-diethoxy -Selected from the group consisting of 1-ethyl-2-methylpropene. These compounds can also be used in commercial grades and, if necessary, prepared from α,β-unsaturated aldehydes and anhydrous acetic acid according to the method described in Bull, Soc, Chim, France, 1961, p. 1194 to 1198. These compounds contain isomers.

In the alkenylene diacetate represented by the general formula (VI), R ¹ and R ² may also be connected to each other to form a cyclic group together with the carbon atoms at the 2-position and 3-position of the propenyl group, as such The preferred cyclic group includes cyclopentyl ring, cyclohexyl ring, etc., preferably cyclohexyl ring.

Examples of the α,β-unsaturated aldehydes used in the production of alkenylene diacetates include acrolein, methacrolein, crotonaldehyde, α,β-dimethylacrolein, and α-ethylpropene. Aldehyde, β-ethylacrolein, β-propylacrolein, α-cyclohexylacrolein, etc., preferably acrolein, methacrolein, crotonaldehyde, more preferably methacrolein.

The catalyst boron halide compound (a) used in the method of the present invention can enumerate for example: boron fluoride, boron trifluoride diethyl ether coordination compound, boron trifluoride tetrahydrofuran coordination compound, boron trifluoride acetate complex salt, As boron trifluoride dihydrate, boron trifluoride-n-butyl ether complex, etc., boron trifluoride ether complex and boron trifluoride acetate complex are preferably used. Commercially available grades of these compounds can be used.

In addition, the triflate compound (b) of a Group 11 element for catalyst is preferably selected from copper triflate and silver triflate.

Furthermore, the halogen compound (c) of Group 12 elements for the catalyst includes zinc fluoride, zinc chloride, zinc bromide, zinc iodide, cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide, mercury fluoride , mercuric chloride, mercuric bromide, and mercuric iodide, among these, zinc halogen compounds are preferably used, and zinc chloride is more preferably used.

In addition, trifluoromethanesulfonate compounds and halogen compounds of tin and atomic numbers of 58, 66-71 lanthanide elements for catalysts and halogen compounds (d) include tin trifluoromethanesulfonate, tin fluoride, tin chloride, bromide Tin, tin iodide, cerium fluoride, cerium chloride, cerium bromide, cerium iodide, cerium triflate, dysprosium fluoride, dysprosium chloride, dysprosium bromide, dysprosium iodide, trifluoromethanesulfonic acid Dysprosium, holmium fluoride, holmium chloride, holmium bromide, holmium iodide, holmium triflate, erbium fluoride, erbium chloride, erbium bromide, erbium iodide, erbium triflate, fluoride Thulium, thulium chloride, thulium bromide, thulium iodide, thulium triflate, ytterbium fluoride, ytterbium chloride, ytterbium bromide, ytterbium iodide, ytterbium triflate, lutetium fluoride, chloride Lutetium, lutetium bromide, lutetium iodide, lutetium trifluoromethanesulfonate, etc., hydrates of these compounds, etc. Among these, tin chloride, tin triflate, erbium triflate, thulium triflate, ytterbium chloride, ytterbium triflate or lutetium triflate are preferably used, More preferably tin chloride or ytterbium chloride is used.

In the method of the present invention, the catalyst is preferably used in an amount of 0.005 to 1 mol or less, more preferably 0.01 to 0.5 mol, more preferably 0.01 to 0.2 mol, based on 1 mol of alkenylene diacetate. If the amount of catalyst added exceeds 1 mole, it is necessary to carry out complex operations such as recovery and decomposition of the catalyst after the reaction is over, discarding, etc., which has the disadvantage of implementing the method of the present invention in industrial applications. In addition, if the amount of catalyst added is less than 0.005 mole, it cannot The reaction is completed within a practical time, for example, within 24 hours.

The reaction in the production method of the present invention can also be carried out in a solvent, but is preferably carried out without a solvent. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, and aromatic halogenated hydrocarbons, or aliphatic halogenated hydrocarbons such as methylene chloride and dichloroethane, and the like can be used.

The reaction temperature in the method of the present invention can be appropriately set according to the type and concentration of the raw material compound and catalyst, but generally, it is preferably -10 to 80°C, more preferably 0 to 60°C. The reaction time in the method of the present invention can be appropriately set according to the above-mentioned raw material compound, the type and concentration of the catalyst, and the reaction temperature, but generally, it is preferably 0.5 to 24 hours, more preferably 0.5 to 12 hours.

The reaction atmosphere in the method of the present invention is not particularly limited, but it is generally preferred to be in a gas that does not react with the raw material compound (compound of general formula (I) and (II), the above-mentioned catalyst and the reaction compound, such as: nitrogen, and It is carried out in an atmosphere or a stream of one or more inert gases such as argon. In addition, although reaction pressure can be performed under usual atmospheric pressure, it is not limited to this.

The 1-acetoxy-3-(substituted phenyl)propene compound synthesized according to the method of the present invention is processed from the reaction mixture after the reaction with the usual separation and recovery procedures, such as extraction, concentration, and filtration. Separation and recovery are carried out, and if necessary, the recovery is subjected to purification treatments such as distillation, recrystallization, and various chromatography methods for purification.

In the general formula (I) representing the 1-acetoxy-3-(substituted phenyl)propene compound synthesized according to the method of the present invention, R ¹ and R ² represent a hydrogen atom or a C ₁ -C ₁₀ alkyl group, preferably At least one of R ¹ and R ² represents a C ₁ -C ₁₀ alkyl group. The C ₁ -C ₁₀ alkyl groups represented by R ¹ and R ² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, which include various isomer. The alkyl groups represented by R ¹ and R ² are preferably methyl groups.

In the general formula (I), the alkyl groups represented by ^R1 and ^R2 may also be connected (bonded) to each other at their ends, and together form a cyclic group with the carbon atoms at the 1-position and 2-position of the propyl group, as the Cyclic groups include cyclopentyl ring, cyclohexyl ring, etc., preferably cyclohexyl.

In the substituted phenyl groups of the general formulas (II) and (III) represented by A in the compound of the general formula (I), R ³ and R ⁴ each independently represent a C ₁ -C ₄ alkyl group, and m represents 0 or An integer of 1 to 4, n represents an integer of 1 to 5, and k represents an integer of 1 or 2. The C ₁ -C ₄ alkyl groups represented by R ³ and R ⁴ include methyl, ethyl, propyl, and butyl, and each includes isomers. The C ₁ -C ₄ alkyl group is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl.

Among the compounds of general formula (I) prepared according to the method of the present invention, the 1-acetoxy-3-(substituted phenyl)propene compound represented by the following general formula (VII) is a novel compound;

(In the above formula (VII), ^R1 and ^R2 are as described above, and B represents one selected from the group of substituted phenyl groups represented by the following formulas (VIII) and (IX),

In formulas (VIII) and (IX), R ³ , R ⁴ and k are as described above).

In the 1-acetoxy-3-(substituted phenyl)propene compound of the general formula (I) of the present invention, when A in the general formula (I) represents a substituted phenyl group of the general formula (III), preferably from the above-mentioned It is selected from 1-acetoxy-3-(3,4-C ₁ -C ₂ alkylenedioxyphenyl)propene represented by the general formulas (X) and (XI). In this case, in the general formulas (X) and (XI), compounds in which R ¹ represents a hydrogen atom and R ² represents a methyl group are preferred.

In addition, in the general formula (I) representing the 1-acetoxy-3-(substituted phenyl)propene compound of the present invention, when A represents a substituted phenyl group of the general formula (II), the substituted phenyl group (II) Preferred are 4-methoxyphenyl, 2,5-dimethoxyphenyl, and 3,4-dimethoxyphenyl.

Thus, the 1-acetoxy-3-(substituted phenyl)propene compound of general formula (I) of the present invention is preferably 1-acetoxy-2-methyl-3-(3,4-methylenedioxy phenyl)propene, 1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene, 1-acetoxy-2-methyl-3-(4- Methoxyphenyl)propene, 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene, 1-acetoxy-2-methyl-3-(3 , 4-dimethoxyphenyl) propene.

Example

The present invention is further illustrated according to the following examples, but the scope of the present invention is not limited by these

limited by the examples.

Also, the yield of 1-acetoxy-2-methyl-3-(substituted phenyl)propene was calculated based on 3,3-diacetoxy-2-methylpropene.

Example 1

In an argon atmosphere, 1,2-methylenedioxybenzene (6.83 g, 56.0 mmol) and 3,3-diacetoxy- A mixed solution of 2-methylpropene (1.05 g, 5.6 mmol) was mixed with boron trifluoride diethyl ether complex (74 mg, 0.52 mmol). The mixture was stirred at 23° C. for 1 hour, ethyl acetate (50 ml) was mixed into the resulting reaction solution, the organic layer formed in the reaction solution was separated, washed three times with water (50 ml), and dried over anhydrous sodium sulfate , and the solvent was distilled off. The residue was subjected to silica gel column chromatography, and 1-acetoxy-2-methyl-3-(3,4-methylenedioxy 1.15 g of phenyl)propene was collected as white crystals. The isolated yield of the obtained target compound was 88%.

The physical property values of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene are expressed as follows:

¹ H-NMR (300MHz, CDCl ₃ ) δ = 1.56 (3H, d, J = 1.5Hz), 2.15 (3H, s), 3.18 (2H, s), 5.92 (2H, s), 6.63 (1H, dd , J=7.8Hz, J=1.5Hz), 6.67 (1H, d, J=1.5Hz), 6.72 (1H, d, J=7.8Hz), 7.02 (1H, q, J=1.5Hz).

¹³ C-NMR (75.5 MHz, CDCl ₃ ) δ=13.43, 20.78, 40.05, 100.86, 108.10, 109.10, 121.31, 121.70, 131.24, 132.79, 146.08, 147.69, 168.26.

Elemental analysis:

C(%)H(%)

Calculated for C ₁₃ H ₁₄ O ₄ 66.666.02

Measured value 66.716.16

Example 2

In an argon atmosphere, 1,2-methylenedioxybenzene (6.83 g, 55.97 mmol) and 3,3-diacetoxy- A mixed solution of 2-methylpropene (0.96 g, 4.88 mmol) was mixed with a boron trifluoride diethyl ether complex (77 mg, 0.54 mmol). The mixed solution was stirred at 23° C. for 1 hour, acetonitrile (100 ml) was mixed with the obtained reaction solution, the mixture was subjected to high performance liquid chromatography, and the reaction solution was analyzed by the absolute calibration curve method. As a result, the yield of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 97.1%. In addition, 5.86 g of unreacted 1,2-methylenedioxybenzene was contained in the reaction liquid.

Embodiment 3～6

In each of Examples 3 to 6, the reaction and analysis were carried out in the same manner as in Example 2. However, the amount of 1,2-methylenedioxybenzene, 3,3-diacetoxy-2-methylpropene, and boron trifluoride ether complex used, the reaction temperature and the reaction time are changed as follows: Recorded in Table 1. The results are shown in Table 1.

Table 1 Compound 1(mmol) ^(*)1 Compound 2(mmol) ^(*)2 BF ₃ ·Et ₂ O(mmol) ^(*)4 Reaction temperature (°C) Reaction time (h) Yield of Compound 3 (%) ^(*)3 Example 3 27.99 5.55 0.54 0 2 84.6 Example 4 27.94 5.55 0.56 twenty three 1 89.3 Example 5 27.94 5.55 0.27 twenty three 3 86.8 Example 6 55.95 5.61 5.58 twenty three 0.5 93.8

[Note] (*) ₁ Compound 1: 1,2-methylenedioxybenzene

(*) ₂ Mixture 2: 3,3-diacetoxy-2-methylpropene

(*) ₃ Compound 3: 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene

(*) ₄ BF ₃ ·Et ₂ O: Boron trifluoride diethyl ether complex

Comparative example 1

In an argon atmosphere, titanium tetrachloride (1.28 g, 6.7 mmol) was added to a 25 ml three-necked flask, and a boron trifluoride diethyl ether complex (0.017 g, 0.12 mmol) was mixed thereinto. At an internal temperature of 8 to 12°C, 1,2-methylenedioxybenzene (3.27 g, 26.8 mmol) was added dropwise to the above mixture over 60 minutes, and then 100% by mass of 3 , a mixture of 3-diacetoxy-2-methylpropene (1.05 g, 6.1 mmol) and 1,2-methylenedioxybenzene (0.75 g, 6.1 mmol) was mixed. The resulting mixture was stirred at an internal temperature of 8 to 10°C for 30 minutes, 6N-hydrochloric acid (10 ml) and dichloromethane (10 ml) were mixed thereinto, followed by stirring for 30 minutes. The insoluble matter was filtered off from the obtained mixture, dichloromethane was mixed with the filtrate for extraction treatment, the obtained organic layer was separated, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained liquid was filtered and concentrated to obtain 3.16 g of crude product. This was supplied to high performance liquid chromatography and analyzed by the absolute calibration curve method. As a result, the yield of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 43.1%, and 1.40 g of unreacted 1 , 2-methylenedioxybenzene.

Comparative example 2

In an argon atmosphere, titanium tetrachloride (0.10 g, 0.5 mmol) was added to a 25 ml three-necked flask. At an internal temperature of 4 to 5°C, 3,3-diacetoxy-2-methylpropene (0.94 g, 5.0 mmol) with a content of 91.7% by mass was added dropwise thereto and mixed, and then 1,2 - Methylenedioxybenzene (6.11 g, 50.0 mmol) was mixed. The resulting reaction mixture was warmed to 23°C and stirred for 18 hours. 20 g of ethanol was added to the obtained reaction liquid, this was subjected to high performance liquid chromatography, and the product was analyzed by the absolute calibration curve method. As a result, the yield of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 9.8%.

Example 7

In an argon atmosphere, a mixed solution of 1,2-methylenedioxybenzene (6.83 g, 56.0 mmol) and zinc chloride (152 mg, 1.12 mmol) was added to a 20 ml flask at 20°C, and mixed therein 3,3-diacetoxy-2-methylpropene (0.96 g, 5.60 mmol) with a content of 100% by mass. After stirring the mixed solution at an internal temperature of 23°C for 3 hours, acetonitrile (85 ml) was mixed with the obtained reaction solution, the mixed solution was subjected to high performance liquid chromatography, and the reaction solution was analyzed by the absolute calibration curve method. As a result, the yield of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 88.3%. In addition, 6.06 g of unreacted 1,2-methylenedioxybenzene was contained in the reaction liquid.

Example 8

In an argon atmosphere, at 20°C, a mixed solution of 1,2-methylenedioxybenzene (2.44 g, 20.0 mmol) and copper trifluoromethanesulfonate (72 mg, 0.20 mmol) was added to a 25 ml flask, 3,3-diacetoxy-2-methylpropene (0.38 g, 2.0 mmol) was mixed therein at a content of 100% by mass. After stirring the mixed solution at an internal temperature of 22°C for 6 hours, ethanol (10 ml) was mixed with the resulting reaction solution, which was subjected to high performance liquid chromatography, and the reaction solution was analyzed by the absolute calibration curve method. As a result, the yield of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 84.0%. In addition, 2.17 g of unreacted 1,2-methylenedioxybenzene was contained in the reaction liquid.

Examples 9-11

In each of Examples 9 to 11, the same reaction as in Example 7 was carried out. However, the amounts of 1,2-methylenedioxybenzene, 3,3-diacetoxy-2-methylpropene, and zinc chloride used, and the reaction time were changed as shown in Table 2. The results are shown in Table 2.

Table 2 Compound 1(mmol) ^(*)1 Compound 2(mmol) ^(*)2 Zinc chloride (mmol) Reaction temperature (°C) Reaction time (h) Yield of Compound 3 (%) ^(*)3 Example 9 55.97 5.95 0.54 twenty three 6 82.1 Example 10 55.88 5.58 2.81 twenty three 1 90.0 Example 11 27.96 5.62 1.16 twenty three 2 81.9

[Note] (*) ₁ Compound 1: 1,2-methylenedioxybenzene

(*) ₂ Mixture 2: 3,3-diacetoxy-2-methylpropene

(*) ₃ Compound 3: 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene

Example 12

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (19.22 g, 100 mmol) and anisole (108.14 g, 1.0 mol). At an internal temperature of 24°C, a boron trifluoride diethyl ether complex (1.42 g, 10 mol) was mixed therein over 2 minutes, and the mixture was stirred at an internal temperature of 24 to 25°C for 1 hour to react. After the reaction, the obtained reaction solution was washed twice with 20 ml of water, and then washed with 20 ml of saturated brine. The organic layer obtained by liquid separation was distilled under reduced pressure (20mmHg, 55-57°C), and the residue was purified by silica gel column chromatography (eluting solvent: hexane/ethyl acetate=10/1) to obtain the target compound 1 as a colorless liquid -Acetoxy-2-methyl-3-(4-methoxyphenyl)propene. The yield thereof was 93.4%, and the yield thereof was 20.58 g.

Example 13

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (1.92 g, 10 mmol) and hydroquinone dimethyl ether ( 13.82 g, 100 mmol). At an internal temperature of 54°C, a boron trifluoride ether complex (0.14 g, 1 mmol) was mixed therein over 1 minute, and stirred at an internal temperature of 53 to 54°C for 1 hour to react. After the reaction was completed, 150 ml of ethyl acetate was added to the reaction solution, followed by washing twice with 20 ml of saturated brine. After liquid separation of the reaction solution, the obtained organic layer was distilled under reduced pressure (20 mmHg, 55-57° C.), and the residue was purified by silica gel column chromatography (elution solvent: hexane/ethyl acetate=10/1) to obtain The target product, 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene, was a colored solid (yield 77.4%, yield 1.94 g).

The physical property values of 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene are expressed as follows:

¹ H NMR (300MHz, CDCl ₃ ) δ=1.63(3H,d,J=1.5Hz), 2.13(3H,s), 3.26(2H,s), 3.75(3H,s), 3.77(3H,s) , 6.70~6.74 (2H, m), 6.78 (1H, d, J=9.6Hz), 6.99 (1H, q, J=1.5Hz).

¹³ C NMR (75.5 MHz, CDCl ₃ ) δ: 13.75, 20.76, 33.73, 55.66, 56.06, 111.57, 120.58, 128.67, 131.58, 151.98, 153.55, 168.17.

HRMS ₍ EI) (M ⁺ ) calcd _{for C14H18O4} : 250.1205, found: 250.1198

Example 14

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (1.92 g, 10 mmol) and hydroquinone dimethyl ether ( 13.82 g, 100 mmol). At an internal temperature of 54°C, a boron trifluoride ether complex (0.14 g, 1 mmol) was mixed therein over 1 minute, and stirred at an internal temperature of 53 to 54°C for 1 hour to react. After the reaction finished, the reaction solution was quantitatively analyzed using high performance liquid chromatography, and the output of 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene was 2.16g (yield rate 86.0%).

Example 15

In an argon atmosphere, 1,2-dimethoxybenzene (69.2 g, 500 mmol) and 3,3-diacetoxy-2-methyl with a content of 89.6% by mass were added to a 100 ml 4-necked flask. Propylene (9.61 g, 50 mmol) was mixed with zinc chloride (1.36 g, 10 mmol) at an internal temperature of 24 to 25°C. The internal temperature was 25 to 26° C., and the mixed solution was stirred for 1.5 hours to react, and the reaction solution was washed 3 times with 50 ml of saturated saline. Separate the organic layer for vacuum distillation (8-10mmHg, 80-84°C), and purify the distillation residue by silica gel column chromatography (elution solvent: hexane/ethyl acetate=10/1) to obtain a colorless liquid The product 1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene (yield 95.1%, yield 11.9 g).

Example 16

In an argon atmosphere, 1,2-dimethoxybenzene (13.82 g, 100 mmol) and 92.0% by mass of 3,3-diacetoxy-2-methyl Propylene (1.87g, 10mmol), to which was added boron trifluoride ether complex (0.142g, 1mmol) at an internal temperature of 18-19°C. The resulting mixed solution was stirred at an internal temperature of 22 to 23° C. for 2 hours. After the reaction, the reaction solution was quantitatively analyzed by high-performance liquid chromatography. The result was the target 1-acetoxy-2-methyl-3-( The yield of 3,4-dimethoxyphenyl)propene was 94.4% (yield 2.36 g).

Comparative example 3

In an argon atmosphere, titanium tetrachloride (1.18g, 6.2mmol) was added to a 3-necked flask with a volume of 25ml, and a boron trifluoride ether complex (0.016g, 0.11mmol) was mixed therein. ~12°C, 1,2-dimethoxybenzene (3.40 g, 24.6 mmol) was added dropwise thereto over 30 minutes, and then, 100% by mass of 3,3-diacetoxy- Mixture of 2-methylpropene (0.96 g, 5.6 mmol) and 1,2-dimethoxybenzene (0.77 g, 5.6 mmol). The resulting mixture was stirred at an internal temperature of 8-10°C for 60 minutes, then added with 6N hydrochloric acid (10 ml) and dichloromethane (10 ml) and stirred for 30 minutes. The insoluble matter in the obtained reaction solution was filtered off, extracted with dichloromethane, the organic layer was washed with water and saturated brine, and dried over Na ₂ SO ₄ . After the obtained reaction solution was filtered, the filtrate was concentrated to obtain 4.54 g of a crude product. Quantitative analysis by high performance liquid chromatography showed that the yield of the target 1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene was 12.0% (yield 0.18g) .

In addition, the reaction liquid was brown, and a large amount of by-products were confirmed by high-performance liquid chromatography analysis.

Example 17

In an argon atmosphere, add ytterbium tri(fluoro)methanesulphonate (1.86 g, 3 mmol) to a 100 ml 3-necked flask, and mix 1,2-methylenedioxybenzene (61.38 g, 502.6 mmol). Mix 3,3-diacetoxy-2-methylpropene (19.30 g, 100.0 mmol) at an internal temperature of 38 to 40° C. for 30 minutes with a content of 89.2 mass % in the above liquid mixture, The mixture was stirred at 41°C for 3 hours. The obtained reaction mixture was washed three times with 16 ml of water, and the water layer after each washing was concentrated to dryness to recover ytterbium trifluoromethanesulfonate. The organic layer after quantitative washing with high performance liquid chromatography, the output of 1-acetoxy group-2-methyl-3-(3,4-methylenedioxyphenyl)propene is 19.57g (yield 83.6%) ).

Example 18

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.44 g, 17.8 mmol) and 1,2-methylenedioxy phenylbenzene (12.2 g, 100.0 mmol). At an internal temperature of 39°C, ytterbium trichloride·hexahydrate (0.23 g, 0.6 mmol) was added thereto, and the resulting reaction solution was stirred at an internal temperature of 39 to 40°C for 3 hours. The resulting reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography. The output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.89g (yield rate of 93.1%).

Example 19

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Benzene (12.212g, 100.0mmol), mixed with ytterbium trifluoromethanesulfonate (the recovered product of Example 17: 0.37g, 0.6mmol) at an internal temperature of 38°C, and the resulting reaction solution was heated at an internal temperature of 39°C to Stir at 40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.64g (yield rate of 77.7%).

Example 20

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with tin trifluoromethanesulfonate (0.25 g, 0.6 mmol) at an internal temperature of 38°C, and the resulting reaction mixture was stirred at an internal temperature of 39-40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 4.10g (yield rate of 87.6%).

Example 21

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with tin tetrachloride (0.16 g, 0.6 mmol) at an internal temperature of 38°C, and the resulting reaction mixture was stirred at an internal temperature of 39-40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 4.15g (yield rate 88.5%).

Example 22

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with cerium trifluoromethanesulfonate (0.36 g, 0.6 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.64g (yield rate of 77.7%).

Example 23

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Dysprosium trifluoromethanesulfonate (0.37 g, 0.6 mmol) was added to phenylbenzene (12.21 g, 100.0 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.26g (yield 69.6%).

Example 24

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with holmium trifluoromethanesulfonate (0.37 g, 0.6 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.56g (yield 76.1%).

Example 25

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with lutetium triflate (0.37 g, 0.6 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The obtained reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography, the output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.91g (yield 83.5%).

Example 26

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with thulium trifluoromethanesulfonate (0.370 g, 0.6 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The resulting reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography. The output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.89g (yield rate of 82.9%).

Example 27

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and 1,2-methylenedioxy Phenylbenzene (12.21 g, 100.0 mmol) was mixed with erbium trifluoromethanesulfonate (0.37 g, 0.6 mmol) at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The resulting reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography. The output of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 3.77g (yield rate 80.5%).

Example 28

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and anisole (10.82 g, 100.0 mmol), and copper trifluoromethanesulfonate (0.22 g, 0.6 mmol) was mixed therein at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The resulting reaction solution was diluted with acetonitrile, and quantified by high performance liquid chromatography. The yield of 1-acetoxy-2-methyl-3-(4-methoxyphenyl)propene was 4.09g (yield 92.7%) .

Example 29

In an argon atmosphere, 3,3-diacetoxy-2-methylpropene (3.86 g, 20.0 mmol) and anisole (11.0 g, 101.8 mmol), and ytterbium trifluoromethanesulfonate (0.37 g, 0.6 mmol) was mixed therein at an internal temperature of 38°C. The resulting reaction mixture was stirred at an internal temperature of 39 to 40°C for 3 hours. The resulting reaction solution was diluted with acetonitrile and quantified by high performance liquid chromatography. The yield of 1-acetoxy-2-methyl-3-(4-methoxyphenyl)propene was 4.15 g (yield 94.2%).

Example 30

In an argon atmosphere at 24°C, 1,2-ethylenedioxybenzene (content: 97% by mass, 7.04g, 51.7mmol) and 3,3-diacetoxy- A boron trifluoride ether complex (71 mg, 0.5 mmol) was added to a mixed solution of 2-methylpropene (89.2% by mass, 0.97 g, 5.0 mmol). After stirring at an internal temperature of 24°C for 2 hours, ethyl acetate (50 ml) was added to the reaction solution, and the obtained organic layer was washed twice with water (50 ml), dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was subjected to silica gel column chromatography, and the oily product 1-acetoxy-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene 0.97g. The isolated yield was 78.2%.

The physical property values of 1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene are expressed as follows:

¹ H-NMR (300MHz, CDCl ₃ ) δ = 1.59 (3H, d, J = 1.5Hz), 2.14 (3H, s), 3.15 (2H, s), 4.23 (4H, s), 6.64 (1H, dd , J=8.1Hz, J=2.0Hz), 6.69 (1H, d, J=2.0Hz), 6.77 (1H, d, J=8.1Hz), 7.02 (1H, q, J=1.5Hz).

HRMS (EI) (M ⁺ ) calcd _{for C14H16O4} : 248.1049, found: _248.1051

Industrial Utilization Possibility

The method of the present invention can easily prepare 1-acetoxy-3-(substituted phenyl)propene compounds useful as intermediates of spices, pharmaceuticals, pesticide products and other organic synthetic drugs with high yield. Therefore, the production method of the 1-acetoxy-3-(substituted phenyl)propene compound of the present invention has high industrial applicability. Furthermore, the 1-acetoxy-3-(substituted phenyl)propene compounds obtained according to the method of the present invention include novel compounds.

Claims (15)

1, the preparation method of 1-acetoxy-3-(substituted-phenyl) propen compounds, it is characterized in that, in order to prepare 1-acetoxy-3-(substituted-phenyl) propen compounds with following general formula (I) expression, be to contain by (a) halogenation boron compound, (b) the trifluoromethanesulfonic acid salt compound of 11 family's elements in the periodic table of elements, (c) halogen compounds of 12 family's elements in the periodic table of elements, (d) tin or ordination number are 58, under the existence of the catalyzer of at least a compound of selecting in the group that the trifluoromethanesulfonic acid salt compound of 66～71 lanthanon and halogen compounds constitute, make from following general formula (IV) and reach one and the represented alkylene group diacetate esters compound reaction of selecting 1 group of (V) represented benzene compound of following general formula (VI);

(in following formula (I), R ¹And R ²Represent from hydrogen atom independently of one another and have one that selects the group that alkyl constituted of 1～10 carbon atom, wherein R ¹And R ²Also can interconnect and 2 of propenyl and 3 carbon atom form cyclic group jointly, A represents from following formula (II) and of (III) selecting in the substituted-phenyl the represented group,

R ³And R ⁴Expression independently of one another has the alkyl of 1～4 carbon atom, and m represents 0 or 1～4 integer, and n represents 1～5 integer, and k represents 1 or 2 integer);

And

(at following formula (IV) and (V), R ³And R ⁴And n, m and k are as previously mentioned);

(in following formula (VI), R ¹And R ²As previously mentioned).

2, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned general formula (IV) is selected from methyl-phenoxide, veratrole, hydroquinone dimethyl ether, reaches phloroglucinol trimethyl ether, reaches hydroxyl Resorcinol three methyl ethers.

3, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented benzene compound of above-mentioned logical formula V is selected from 1,2-methylenedioxybenzenes and ethylenedioxy benzene.

4, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the represented alkylene group diacetate esters of above-mentioned general formula (VI) is selected from 3,3-diacetoxy-2-methacrylic, 3,3-diacetoxy propylene, 3,3-diethoxy-1-methacrylic, 3,3-diacetoxy-2-ethyl propylene, 3,3-diethoxy-1-ethyl propylene and 3,3-diethoxy-1-ethyl-2-methacrylic.

5, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, in above-mentioned reaction, above-mentioned benzene compound and above-mentioned alkylene group diacetate esters use mol ratio 1～50: 1.

6, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, with respect to 1 mole of above-mentioned alkylene group diacetate esters, the usage quantity of above-mentioned catalyzer is 0.005～1 mole.

7, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the employed halogenation boron compound of above-mentioned catalyzer (a) is selected from the group that boron fluoride, boron trifluoride diethyl ether coordination compound, boron trifluoride tetrahydrofuran (THF) coordination compound, boron trifluoride acetic acid complex salt, boron trifluoride dihydrate and boron trifluoride-n-butyl ether coordination compound constitutes.

8, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the trifluoromethanesulfonic acid salt compound (b) of the employed 11 family's elements of above-mentioned catalyzer is selected from copper trifluoromethanesulfcomposite and silver trifluoromethanesulfonate.

9, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the halogen compounds (c) of the employed 12 family's elements of above-mentioned catalyzer is selected from zinc fluoride, zinc chloride, zinc bromide, zinc iodide, cadmium fluoride, Cadmium chloride fine powder, cadmium bromide, cadmium iodide, hydrogen fluoride, mercury chloride, mercuric bromide and red mercury iodide.

10, the preparation method of the described 1-acetoxy-3 of claim 5-(substituted-phenyl) propen compounds, employed tin of above-mentioned catalyzer and ordination number are the fluoroform sulphonate of 58,66～71 lanthanon and trifluoromethanesulfonic acid salt compound, fluorochemical, muriate, bromide and the iodide that halogen compounds (d) is selected from tin, cerium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

11, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, above-mentioned being reflected in the atmosphere that gas constituted that does not react with above-mentioned general formula (IV), (V) and (VI) compound, above-mentioned catalyzer and resultant of reaction carried out.

12, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned formula (I) is selected from the compound of following general formula (VII) expression;

(in above-mentioned formula (VII), R ¹And R ²As previously mentioned, B is that expression is selected from following formula (VIII) and (IX) 1 in represented 1 group the substituted-phenyl,

During formula (VIII) reaches (IX), R ³And R ⁴And k as previously mentioned).

13, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) is selected from following formula (X) and reaches (XI):

And

1-acetoxy-3-(3, the alkylenedioxy group phenyl of 4-C1～C2) propylene of expression.

14, the preparation method of the described 1-acetoxy-3 of claim 12-(substituted-phenyl) propen compounds, in above-mentioned formula (X) or (XI), R ¹The expression hydrogen atom, R ²The expression methyl.

15, the preparation method of the described 1-acetoxy-3 of claim 1-(substituted-phenyl) propen compounds, the compound of above-mentioned general formula (I) is selected from 1-acetoxyl group-2-methyl-3-(3, the 4-methylenedioxyphenyl) propylene, 1-acetoxyl group-2-methyl-3-(3,4-ethylenedioxy phenyl) propylene, 1-acetoxyl group-2-methyl-3-(4-p-methoxy-phenyl) propylene, 1-acetoxyl group-2-methyl-3-(2, the 5-Dimethoxyphenyl) propylene and 1-acetoxyl group-2-methyl-3-(3, the 4-Dimethoxyphenyl) propylene.