KR102352033B1 - Process for preparing tetrahydroindenes - Google Patents

Abstract

The manufacturing method according to the present invention is a bis(indenyl) complex by performing a hydrogenation reaction of a bis(indenyl) complex under a low hydrogen pressure and then performing a hydrolysis reaction under an aqueous alkali solution condition, which is much milder ( It is to easily prepare tetrahydroindene derivatives introduced with various substituents through reaction under mild) conditions, and can be usefully used for mass synthesis in high yield under safe and efficient process conditions.

Description

Method for producing tetrahydroindene derivatives {PROCESS FOR PREPARING TETRAHYDROINDENES}

The present invention relates to a method for preparing a tetrahydroindene derivative.

Tetrahydroindene derivatives are important precursors of metallocene complexes used as polymerization catalysts. To this end, the tetrahydroindene derivative can be reacted with a transition metal, in particular a zirconium salt and a metallocenium ion former to obtain the corresponding metallocene complex.

Such tetrahydroindene derivatives can be prepared by various methods. Usually, the intermediate indanone derivative is prepared and then converted to the corresponding indene derivative by reduction and dehydration reactions. 5-membered rings by, for example, reaction with malonic acid esters, alkaline hydrolysis of diesters, thermal decarboxylation of residual carboxyl groups, chlorination reactions and intramolecular Friedel-Crafts acylation reactions. A method for synthesizing benzindanone by forming This synthesis method is technically very complex because it is performed in multiple steps.

Also, a method for synthesizing an indanone derivative in which a benzene derivative is reacted with a substituted acrylic acid ester in liquid hydrogen fluoride to form a 5-membered ring is known. Also known is a method for producing 2-methylbenzindanone, in which naphthalene is _{reacted with methacrylic anhydride in the presence of BF 3 /hydrogen fluoride.} This synthetic route also poses considerable technical complexity due to the problem of handling highly toxic hydrofluoric acid. Also known is a method for synthesizing indanone by reacting a benzene derivative with α-haloalkylpropionyl halide, preferably α-bromoisobutyryl bromide.

However, the disadvantages of these syntheses are that they are complex multi-step processes, produce a large amount of halogen-containing wastes, and use some highly toxic reactants.

Therefore, in practical application of tetrahydroindene derivatives, various substituents are introduced and large-capacity synthesis is possible. Research on the process is continuously required.

The present invention is to provide a method for preparing a tetrahydroindene derivative.

In order to solve the above problems, the present invention comprises the steps of reacting a compound of Formula 1 with hydrogen in the presence of a catalyst containing a transition metal of Groups 8 to 10 to generate a compound of Formula 2 below (step 1); And it provides a method for producing a tetrahydroindene derivative, comprising the step of reacting the compound of formula (2) under an aqueous alkali solution condition to produce a compound of formula (3) (step 2).

[Formula 1]

[Formula 2]

[Formula 3]

during the meal,

R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', and R ₃ ' are the same or different from each other and each independently represent hydrogen, a C 1 to C 30 hydrocarbyl group, or a C 1 to C 30 hydrocarbyloxy group. And it is selected from the group consisting of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

M is a Group 4 transition metal,

Q ₁ , Q ₂ are the same or different from each other, and each independently represents a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, or a C 1 to C 30 hydrocarbyloxy group. , a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, —SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms.

Hereinafter, the present invention will be described in detail for each step.

bis ( Indenyl ) hydrogenation reaction step of complex compound (step 1)

The present invention is characterized in that tetrahydroindene derivatives introduced with various substituents are synthesized in high yield from indene derivatives through a reaction under conditions much milder than conventional harsh conditions.

Step 1 is a hydrogenation reaction step in which hydrogen is introduced into all four carbons of the 6-membered ring portion of the benzene ring rather than the 5-membered ring portion of the cyclopentadienyl ring in the indene derivative.

First, in Step 1, the compound of Formula 1 is reacted with hydrogen in the presence of a catalyst containing a transition metal of Groups 8 to 10 to generate a compound of Formula 2 below.

[Formula 1]

[Formula 2]

during the meal,

R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ' are the same or different from each other, and independently hydrogen, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, and It is selected from the group consisting of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,

M is a Group 4 transition metal,

Q ₁ , Q ₂ are the same or different from each other, and each independently represents a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, or a C 1 to C 30 hydrocarbyloxy group. , a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, —SiH ₃ , a hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms.

The R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ' is an example, and each of the R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ' is hydrogen , a straight chain, branched chain, or cyclic alkyl group having 1 to 20 carbon atoms, or a straight chain, branched chain, or cyclic alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms group, or an aralkyl group having 7 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an aryl group having 7 to 30 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkylalkoxy group having 2 to 20 carbon atoms. have. More specifically, R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', and R ₃ ' may each be hydrogen, methyl, n-butyl, phenyl, or p-(t-butyl)phenyl.

The M may be, for example, Zr, Hf, or Ti, respectively.

The Q ₁ , Q ₂ may be, for example, halogen such as chlorine; or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-butyl; Or it may be an alkoxyalkyl group having 2 to 20 carbon atoms, such as t-butoxyhexyl.

In particular, the compound represented by Chemical Formula 1 is a bis (indenyl) complex, and hydrogenation reaction is performed in the presence of a catalyst containing a transition metal of Groups 8 to 10. Since the compound represented by Formula 1 is much more stable than the previously known reactants of the hydrogenation reaction, mass synthesis is possible, and since it has no reactivity with a halogen solvent, it can be used as a solvent for the hydrogenation reaction.

Unless otherwise limited herein, the following terms may be defined as follows.

The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from hydrocarbon, and is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group. It may include a nylaryl group and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. , a straight-chain, branched-chain or cyclic alkyl group such as n-heptyl group and cyclohexyl group; or an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group; or a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- a straight-chain, branched-chain or cyclic alkyl group such as a heptyl group or a cyclohexyl group; Or it may be an aralkyl group such as a phenyl group, a naphthyl group, or an anthracenyl group substituted with an alkyl group as described above.

The hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms may be a hydrocarbyloxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group , a straight-chain, branched-chain or cyclic alkoxy group such as n-hexoxy group, n-heptoxy group, cyclohexoxy group; Alternatively, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

A hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of a hydrocarbyl group are substituted with one or more hydrocarbyloxy groups. Specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyloxyhydrocarbyl group having 2 to 20 carbon atoms or 2 to 15 carbon atoms. More specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-part alkoxyalkyl groups such as a oxymethyl group, a tert-butoxyethyl group, and a tert-butoxyhexyl group; or an aryloxyalkyl group such as a phenoxyhexyl group.

The hydrocarbyl(oxy)silyl group _{is a functional group in which 1 to 3 hydrogens of -SiH 3} are substituted with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms may be a hydrocarbyl (oxy)silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy)silyl group having 1 to 30 carbon atoms is an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group or a dimethylpropylsilyl group. silyl group; Alkoxysilyl groups, such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, or a dimethoxyethoxysilyl group; It may be an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group.

The silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with a silyl group. The silyl group _{may be -SiH 3} or a hydrocarbyl (oxy)silyl group. Specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be a silylhydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the silylhydrocarbyl group having 1 to 20 carbon atoms may be -CH _{2 -SiH 3} , a methylsilylmethyl group, or a dimethylethoxysilylpropyl group.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The sulfonate group has ^a _{structure of -O-SO 2} -R a , and R ^a may be a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfonate group having 1 to 30 carbon atoms may be a methanesulfonate group or a phenylsulfonate group.

A sulfone group having 1 to 30 carbon atoms has a structure of ^{-R b '} -SO ₂ -R ^{b " , wherein R b '} and R ^{b "} are the same as or different from each other, and each independently any one of a C 1 to C 30 hydrocarbyl group. can Specifically, the sulfone group having 1 to 30 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.

On the other hand, in the present invention, the catalyst for hydrogenating the bis (indenyl) complex of Formula 1 is characterized in that it contains a transition metal of Groups 8 to 10. The transition metal catalyst may include, for example, a noble metal, and more specifically, may be Pd, Ru, Rh, or Pt. Meanwhile, the transition metal catalyst may be, for example, one or more of PtO ₂ , Pd/C, Rh/C, or Ru/C. Among them, from the viewpoint of reaction selectivity, PtO ₂ , Pd/C is more preferable.

The addition amount of the transition metal catalyst may be about 0.1 to 50 mol%, or about 1 to 25 mol%, or about 5 to 10 mol%, based on the compound of Formula 1. The addition amount of the transition metal catalyst may be about 0.1 mol% or more in terms of efficiency, and may be about 50 mol% or less in terms of economy.

In addition, by performing step 1 in a low hydrogen pressure range, sufficient stability can be ensured even during mass production. The hydrogen pressure range may be about 50 bar or about 1 to 50 bar, or about 3 to 45 bar, or about 5 to 35 bar. In step 1, the hydrogen pressure may be performed at about 50 bar or less in terms of reaction safety and economy. In addition, in terms of reaction efficiency, the hydrogen pressure may be about 1 bar or more.

The reaction of step 1 is a much milder process compared to the conventional one, and may be performed under temperature conditions of about 0 to 60 ℃, or about 10 to 50 ℃, or room temperature (23 ℃) to about 40 ℃. The reaction of step 1 may be performed at 0 °C or higher in terms of reaction efficiency, and may be performed at about 60 °C or lower in terms of reaction selectivity.

The reaction time of step 1 may be about 1 to 96 hours, or about 3 to 48 hours, or about 12 to 24 hours. The reaction time of step 1 may be about 1 hour or more in terms of reaction efficiency, and may be about 96 hours or less in terms of reaction selectivity and economic feasibility.

On the other hand, the method for preparing the tetrahydroindene derivative of the present invention may further include the step of reacting the compound of formula (a) with alkyl lithium and then reacting it with a compound containing a Group 4 transition metal to produce the compound of formula (1). can

[Formula a]

In the formula, R ₁ , R ₂ , and R ₃ are as described above.

Here, the compound represented by the formula (a) is an indene compound, and is stable at room temperature and air. For example, the indene compound may include indene, 3-butyl-1H-indene, 2-methyl-1H-indene, and 2-methyl -4-phenyl-1H-indene (2-methyl-4-phenyl-1H-indene), etc. are mentioned.

In addition, the compound containing the Group 4 transition metal has a weak characteristic to moisture. The Group 4 transition metal may include, for example, Zr, Ti, Hf, and the like. The Group 4 transition metal compound including the same is preferably TiCl ₄ , ZrCl ₄ , HfCl ₄ and the like. Meanwhile, the transition metal compound may be in a form that further includes Ta, V, Nb, Sc, Y, etc. together with a Group 4 transition metal.

The step of generating the complex compound may be performed under conditions without moisture, and in particular, under conditions of an inert gas such as nitrogen or argon in terms of reaction stability. For example, the compound of Formula 1 may be produced through the reaction represented by Scheme 1 below.

[Scheme 1]

In Scheme 1, R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ', M, Q ₁ , and Q ₂ are the same as described above.

On the other hand, the compound of formula (a) may be prepared through a method or reaction commonly known in the art, and various methods may be applied without particular limitation.

hydrogenated bis ( Indenyl ) hydrolysis reaction step of the complex (step 2)

Step 2 is a step of preparing a tetrahydroindene derivative by reacting the compound of Formula 2 generated through the hydrogen reaction of Step 1 under an aqueous alkali solution condition.

First, through the hydrogenation reaction of step 1 as described above, a hydrogen-substituted compound of Formula 2 is generated.

[Formula 2]

In the formula, R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ', M, Q ₁ , and Q ₂ are the same as described above in step 1.

In addition, the compound of Formula 2 may be reacted under an aqueous alkali solution condition to produce a compound of Formula 3 below.

[Formula 3]

In the formula, R ₁ , R ₂ , R ₃ are the same as described above in step 1.

The compound represented by Formula 3 is a tetrahydroindene derivative and has a stable characteristic at room temperature. Preferably, the tetrahydroindene derivative may have one of the following structural formulas.

,

,

,

,

,

,

The aqueous alkali solution may be, for example, one or more of NaOH, NaHCO ₃ , KOH, Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , or K ₂ PO ₄ .

In addition, the aqueous alkali solution may have a pH of about 7 to 14, or about 8 to 12, or about 9 to 10. The pH of the aqueous alkali solution may be about 7 or more in terms of reaction efficiency, and may be 14 or less in terms of reaction selectivity.

In addition, the reaction temperature of step 2 may be about 0 to 60 ℃, or about 10 to 40 ℃, or room temperature (23 ℃) to about 30 ℃. The reaction temperature of step 2 is preferably about 0 ° C. or higher in terms of efficiency, and may be about 60 ° C. or less in terms of reaction selectivity.

The reaction time of step 2 may be about 1 to 24 hours, or about 3 to 12 hours, or about 6 to 8 hours. The reaction time of step 2 may be about 1 hour or more in terms of efficiency, and may be about 24 hours or less in terms of reaction selectivity and economy.

The reaction pressure of step 2 may be applied within a conventional range known in the art, and may be carried out in a normal pressure range without any particular limitation.

As described above, in the production method according to the present invention, a bis(indenyl) complex is subjected to a hydrogenation reaction under a low hydrogen pressure and then a hydrolysis reaction is performed under an aqueous alkali solution condition. It is a method to easily prepare tetrahydroindene derivatives with various substituents introduced through the reaction under conditions much milder than the conditions, and it can be usefully used for mass synthesis in high yield under safe and efficient process conditions. .

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.

Example One

(Step 1)

In a 100 mL Parr reactor, Bis(indenyl)ZrCl ₂ (strem, about 3.9 g, about 6.9 mmol), dichloromethane (DCM, about 40 mL), and PtO ₂ (about 5 mol%) were added. The inside was filled with H ₂ about 34 bar and stirred at room temperature for about 24 hours. The reaction product was filtered through a glass filter and the filtrate was vacuum dried to obtain a white powdery intermediate, Bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (about 2.6 g, about 5.6 mmol, about 81% yield).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.57~1.71 (4H, m), 1.78~1.88 (4H, m), 2.49~2.61 (4H, m), 5.75~5.82 (4H, m), 5.79 ( 4H, d), 6.27 (2H, t).

(Step 2)

Bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (2 g, 5.0 mmol), Toluene (about 40 mL), and NaHCO ₃ saturated aqueous solution (about 20 mL) prepared in step 1 above was mixed with 100 It was placed in an mL round bottom flask and stirred at room temperature for about 20 hours. The organic layer was separated, and moisture was removed with _{MgSO 4 .} The solvent was dried under reduced pressure to obtain [3a],5,6,7-tetrahydro-4H-indene in the form of a colorless liquid (0.99 g, 8.2 mmol, 82% yield).

¹ H-NMR (300 MHz, CDCl ₃ ): 1.57~1.68 (2H, m), 1.76~1.86 (2H, m), 2.42~2.67 (4H, m), 2.67~2.78 (1H, m), 5.59 ( 1H, s), 5.86 (1H, s), 6.18 (1H, t).

Example 2

(Step 1)

In a 2 L high pressure reactor, Bis(indenyl)ZrCl ₂ (strem, about 80 g, about 200 mmol), dichloromethane (DCM, about 800 mL), and Pd/C (about 5 mol%) were added. The inside _{was filled with about 10 bar of H 2} and stirred at about 40 °C for about 24 hours. The reaction product was filtered through a celite filter and the filtrate was vacuum dried to obtain a white powdery intermediate, Bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (69 g, 170 mmol, 86 % yield). ).

(Step 2)

Bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride (69 g, 170 mmol), Toluene (about 1.5 L), and NaHCO ₃ saturated aqueous solution (about 0.75 L) prepared in step 1 It was put into the L reactor and stirred at room temperature for about 20 hours at a speed of about 200 rpm. The organic layer was separated, and moisture was removed with _{MgSO 4 .} The solvent was dried under reduced pressure to obtain [3a],5,6,7-tetrahydro-4H-indene in the form of a colorless liquid (33 g, 280 mmol, 80 % yield).

Example 3

(Step 1)

In a 100 mL Parr reactor, bis(3-butyl-1H-inden-1-yl)zirconium(IV) chloride (2.9 g, 5.8 mmol), dichloromethane (DCM, 50 mL), PtO ₂ (5 mol%) were added was put in. The inside _{was filled with H 2} 20 bar and stirred at room temperature for 24 hours. The reactant was filtered through a glass filter and the filtrate was vacuum dried to obtain an intermediate in the form of a light green solid, bis(3-butyl-4,5,6,7-tetrahydro-1H-inden-1-yl)zirconium(IV) chloride (2.5 g, 4.9 mmol, 84 % yield, racemic, 1:1 mixture of meso isomer).

¹ H-NMR (500 MHz, C ₆ D ₆ ): 0.88 ppm (t, 6H), 5.22 ppm (s, 1H), 5.26 ppm (s, 1H), 5.68 (s, 1H), 5.78 ppm (s, 1H)

(Step 2)

bis(3-butyl-4,5,6,7-tetrahydro-1H-inden-1-yl)zirconium(IV) chloride (2.5 g, 4.9 mmol), Toluene (40 mL), NaHCO prepared in step 1 _{3 A} saturated aqueous solution (20 mL) was placed in a 100 mL round bottom flask and stirred at room temperature for 20 hours. The organic layer was separated, and moisture was removed with _{MgSO 4 .} The solvent was dried under reduced pressure to obtain 3-butyl-3a,5,6,7-tetrahydro-4H-indene as a pale yellow liquid (1.4 g, 8.2 mmol, 84 % yield).

¹ H-NMR (500 MHz, C ₆ D ₆ ): 0.91 ppm (t, 3H), 1.22-1.81 ppm (m, 9H), 2.18-2.96 ppm (m, 6H), 6.01 (s, 1H), 6.10 ppm (s, 1H)

Example 4

(Step 1)

In a 100 mL Parr reactor, bis(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)zirconium(IV) chloride (10 g, 15 mmol), dichloromethane (DCM) , 40 mL), PtO ₂ (5 mol%) was added. The inside _{was filled with H 2} 20 bar and stirred at room temperature for 24 hours. The reactant was filtered through a glass filter and the filtrate was vacuum dried to obtain a white powdery intermediate, bis(4-(4-(tert-butyl)phenyl)-2-methyl-4,5,6,7-tetrahydro-1H -inden-1-yl)zirconium(IV) chloride was obtained (8.0 g, 12 mmol, 79 % yield, racemic, 1:1 mixture of meso isomer).

¹ H-NMR (500 MHz, C ₆ D ₆ ): 1.26 (s, 9H), 1.27 (s, 9H), 1.45 (s, 3H), 1.46 (s, 3H), 1.54-2.04 (m, 5H) , 2.36-2.56(q, 2H), 2.89-3.17(m, 3H), 3.26-3.38 (s, 1H), 3.69 (t, 2H), 5.41 (s, 1H), 5.58 (s, 1H), 5.60 (s, 1H), 5.82 (s, 1H), 7.22-7.37 (m, 4H), 7.22-7.37 (m, 4H), 7.37-7.52 (m, 4H).

(Step 2)

bis(4-(4-(tert-butyl)phenyl)-2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl)zirconium(IV) chloride (8.0 g, 12 mmol), Toluene (40 mL), and a _{saturated aqueous solution of NaHCO 3} (20 mL) were placed in a 100 mL round bottom flask and stirred at room temperature for 20 hours. The organic layer was separated, and moisture was removed with _{MgSO 4 .} The solvent was dried under reduced pressure to obtain 7-(4-(tert-butyl)phenyl)-2-methyl-3a,5,6,7-tetrahydro-4H-indene in the form of a pale yellow liquid (5.2 g , 20 mmol, 87 % yield as a mixture of isomers).

¹ H-NMR (500 MHz, C ₆ D ₆ ): 1.26 (s, 9H), 1.37-2.70 (m, 8H), 1.85 (s, 3H), 3.62 (s, 1H), 5.98 (s, 1H) , 7.12 (d, 2H), 7.29 (d, 2H)

comparative example One

In Example 1, the reactant of step 1 Bis(indenyl)ZrCl ₂ Instead, (1H-inden-1-yl)lithium was used, and the reaction was carried out in the same manner as in Example 1, except that _{NH 4} Cl was used instead of _{NaHCO 3 as the alkaline component in step 2 [3a],} 5,6,7-tetrahydro-4H-indene was prepared, but it was confirmed that the synthesis yield was not good (0.58 g, 4.8 mmol, 48 % yield).

Claims (14)

reacting the compound of Formula 1 with hydrogen in the presence of a catalyst containing a transition metal of Groups 8 to 10 to produce a compound of Formula 2 below (step 1); and
Comprising the step (step 2) of reacting a compound of Formula 2 below under aqueous alkali solution conditions to produce a compound of Formula 3 below,
Method for preparing tetrahydroindene derivatives:
[Formula 1]

[Formula 2]

[Formula 3]

during the meal,
R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', and R ₃ ' are the same or different from each other and each independently represent hydrogen, a C 1 to C 30 hydrocarbyl group, or a C 1 to C 30 hydrocarbyloxy group. And it is selected from the group consisting of a hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms,
M is a group 4 transition metal,
Q ₁ , Q ₂ are the same or different from each other, and each independently a halogen, a nitro group, an amido group, a phosphine group, a phosphide group, a C 1 to C 30 hydrocarbyl group, a C 1 to C 30 hydrocarbyloxy group, A hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbylsilyl group having 1 to 30 carbon atoms, a hydrocarbyloxysilyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and 1 to 30 carbon atoms one of the sulfonic groups of
According to claim 1,
The R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', and R ₃ ' are each hydrogen, a straight chain, branched chain, or cyclic alkyl group having 1 to 20 carbon atoms, or a straight chain, branched chain having 1 to 20 carbon atoms. , or a cyclic alkoxy group, or an aryl group having 6 to 30 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms, or 7 to 30 carbon atoms of an aryl group, or an alkoxyalkyl group having 2 to 20 carbon atoms, or an alkylalkoxy group having 2 to 20 carbon atoms,
manufacturing method.
According to claim 1,
wherein R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ', R ₃ ' are each hydrogen, methyl, n-butyl, phenyl, or p-(t-butyl)phenyl;
Wherein M is each Zr, Hf, or Ti,
Wherein Q ₁ , Q ₂ are each halogen, methyl, ethyl, n-butyl, or t-butoxyhexyl,
manufacturing method.
According to claim 1,
The transition metal of Groups 8 to 10 is Pd, Ru, Rh, or Pt,
manufacturing method.
According to claim 1,
The aqueous alkali solution is to include NaOH, NaHCO ₃ , KOH, Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , or K ₂ PO ₄ ,
manufacturing method.
According to claim 1,
The aqueous alkali solution has a pH of 7 to 14,
manufacturing method.
According to claim 1,
The addition amount of the transition metal catalyst is 0.1 to 50 mol%,
manufacturing method.
According to claim 1,
The hydrogen pressure of step 1 is 50 bar or less,
manufacturing method.
According to claim 1,
The reaction temperature of step 1 is 0 to 60 ℃,
manufacturing method.
According to claim 1,
The reaction time of step 1 is 1 to 96 hours,
manufacturing method.
According to claim 1,
The reaction temperature of step 2 is 0 to 60 ℃,
manufacturing method.
According to claim 1,
The reaction time of step 2 is 1 to 24 hours,
manufacturing method.
According to claim 1,
Further comprising the step of reacting the compound of formula (a) with alkyl lithium and then reacting with a compound containing a Group 4 transition metal to produce the compound of formula (1),
Manufacturing method:
[Formula a]

In the formula, R ₁ , R ₂ , and R ₃ are the same or different from each other, and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and hydrocarbyloxy having 2 to 30 carbon atoms. It is selected from the group consisting of a hydrocarbyl group.
According to claim 1,
The tetrahydroindene derivative is one of the following structural formula,
manufacturing method.

,

,

,