KR20190085777A - Process for preparing tetrahydroindenes - Google Patents

Abstract

According to a method for preparing tetrahydroindene derivatives, a hydrolysis reaction is performed under the alkali solution condition after a hydrogenation reaction of a bis(indenyl) complex compound is performed under the low hydrogen pressure, so that tetrahydroindene derivatives with various substituents can be easily prepared through a reaction with more mild conditions than existing severe conditions. The tetrahydroindene derivatives can be synthesized in a large quantity with high yield under the stable and efficient process conditions.

Description

PROCESS FOR PREPARING TETRAHYDROINDENES [0002]

The present invention relates to a process for the production of tetrahydroindene derivatives.

Tetrahydroindene derivatives are important precursors of metallocene complexes used as polymerization catalysts. To this end, the tetrahydroidene derivatives can be reacted with transition metals, in particular zirconium salts and metallocenium ion forming compounds, to give the corresponding metallocene complexes.

Such tetrahydroindene derivatives can be prepared by various methods. Typically, intermediates indanone derivatives are prepared and then converted to the corresponding indene derivatives by reduction and dehydration. For example, by reacting with a malonic acid ester, alkali hydrolysis of a diester, thermal decarboxylation of a residual carboxyl group, chlorination reaction and Friedel-Crafts acylation reaction in a molecule, To synthesize benzindanone. This synthesis method is technically very complicated because it is performed in multiple steps.

Further, there is known 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. It is also known to prepare 2-methylbenzindanone, in which naphthalene is reacted with methacrylic anhydride in the presence of BF ₃ / hydrogen fluoride. This synthetic route also involves considerable technical complexity because of the problem of handling highly toxic hydrofluoric acid. Also known is a method of synthesizing indanone by reacting a benzene derivative with an? -Haloalkylpropionyl halide, preferably? -Bromoisobutyryl bromide.

However, a disadvantage of the above synthesis methods is that it is a complicated multi-step process and uses a large amount of halogen-containing waste materials and some toxic reactants.

Therefore, it is possible to easily manufacture the tetrahydroindene derivative in a much mild reaction at a low hydrogen pressure or a low hydrogen pressure so that a large capacity synthesis can be carried out by introducing various substituents in the practical application of the tetrahydroindene derivative There is a continuing need for process research.

The present invention provides a process for producing a tetrahydroindene derivative.

In order to solve the above problems, the present invention relates to a process for producing a compound represented by the following formula (2) by reacting a compound represented by the following formula (1) with hydrogen in the presence of a catalyst containing a transition metal of group 8 to group 10 (step 1); And reacting the compound of formula (2) with an alkali aqueous solution to produce a compound of formula (3) (step 2).

[Chemical Formula 1]

(2)

(3)

Wherein,

R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'are the same or different and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms And a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are the same or different from each other and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms , A hydrocarbyl oxyhydrocarbyl 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.

Bis ( Indeny ) Hydrogenation of the complex (step 1)

The present invention is characterized in that a tetrahydroindene derivative having various substituents introduced thereinto is synthesized at a high yield through a mild condition than an existing harsh condition from an indene derivative.

Step 1 is a hydrogenation step of introducing hydrogen into all four carbon atoms of the six-membered ring portion of the benzene ring which is not the 5-membered ring portion of the cyclopentadienyl ring in the indene derivative.

First, the step 1 is a step of reacting a compound represented by the following formula (1) with hydrogen in the presence of a catalyst containing a transition metal of group 8 to group 10 to produce a compound represented by the following formula (2).

[Chemical Formula 1]

(2)

Wherein,

R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'are the same or different and independently represent hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are the same or different from each other and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms , A hydrocarbyl oxyhydrocarbyl 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.

Wherein R _{1, R 2, R 3, R 1} ', R 2', R 3 ' is wherein R _1, in one example, each of _{R 2, R 3, R 1} ', R 2 ', R 3' are each hydrogen , A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a linear, branched, 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 Or an aralkyl group having 7 to 30 carbon atoms or an aryloxy group having 6 to 30 carbon atoms or an aryl group having 7 to 30 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms or an alkylalkoxy group having 2 to 20 carbon atoms have. More specifically, each of R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'may be hydrogen, methyl, n-butyl, phenyl, or p- (t-butyl) phenyl.

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

Examples of Q ₁ and Q ₂ include halogen such as chlorine; Or a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-butyl and the like; Or an alkoxyalkyl group having 2 to 20 carbon atoms such as t-butoxyhexyl.

In particular, the compound represented by Formula 1 is subjected to a hydrogenation reaction in the presence of a catalyst containing a transition metal of group 8 to group 10 as a bis (indenyl) complex. The compound represented by the formula (1) can be synthesized in a large amount because it is much more stable than a known reaction product of the hydrogenation reaction, and is not reactive with a halogen solvent, and thus can be used as a solvent for a hydrogenation reaction.

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

The hydrocarbyl group is a monovalent functional group having a hydrogen atom removed from a 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, Aryl 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. Specific examples of the hydrocarbyl group having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, , an n-heptyl group, a cyclohexyl group, and other straight, branched or cyclic alkyl groups; An aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group; N-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-pentyl group, n-pentyl group, A straight chain, branched chain or cyclic alkyl group such as a heptyl group and a cyclohexyl group; Or an aralkyl group such as a phenyl group substituted with an alkyl group as described above, a naphthyl group, or an anthracenyl group.

The hydrocarbyloxy group is a functional group in which the 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 preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a n-butoxy group, an iso-butoxy group, , an n-hexoxy group, an n-heptoxy group, a cycloheptoxy group, and other straight-chain, branched-chain or cyclic alkoxy groups; Or an aryloxy group such as a phenoxy group or a naphthalenoxy group.

The hydrocarbyloxyhydrocarbyl group is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with at least one hydrocarbyloxy group. Specifically, the hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyl oxyhydrocarbyl 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 preferably a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an isopropoxymethyl group, an isopropoxyethyl group, an iso-propoxyhexyl group, Alkoxyalkyl groups such as a methoxymethyl group, a tert-butoxyethyl group, and a tert-butoxyhexyl group; Or an aryloxyalkyl group such as a phenoxyhexyl group.

Hydrocarbyl (oxy) group is a silyl functional group is substituted with one to three of the hydrogen -SiH ₃ group one to three dihydro car invoke or hydrocarbyl oxy. 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; An alkoxysilyl group such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group or a dimethoxyethoxysilyl group; An alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group or a dimethoxypropylsilyl group, and the like.

The silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen atom 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 silyl hydrocarbyl group having 1 to 20 carbon atoms may be a silyl hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the silyl hydrocarbyl group having 1 to 20 carbon atoms may be -CH ₂ -SiH ₃ , a methylsilylmethyl group, a dimethylethoxysilylpropyl group, or the like.

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

The sulfonate group may have the structure of -O-SO ₂ -R ^a , wherein 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 methane sulfonate group, a phenyl sulfonate group, or the like.

The sulfone group having 1 to 30 carbon atoms has the structure of -R ^{b '} -SO ₂ -R ^{b "} wherein R ^{b '} and R ^{b "} are the same or different and each independently is any one of hydrocarbyl groups having 1 to 30 carbon atoms . 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.

In the present invention, the catalyst for hydrogenating the bis (indenyl) complex of the formula (1) comprises a transition metal of group 8 to group 10. The transition metal catalyst may include, for example, a noble metal or the like. More specifically, the transition metal catalyst may be Pd, Ru, Rh, or Pt. The transition metal catalyst may be one or more of PtO ₂ , Pd / C, Rh / C, Ru / C, and the like. Among them, PtO ₂ and Pd / C are more preferable in view of reaction selectivity.

The amount of the transition metal catalyst added 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 amount of the transition metal catalyst to be added may be about 0.1 mol% or more in terms of efficiency and about 50 mol% or less in terms of economy.

In addition, the step 1 is carried out in a low hydrogen pressure range, so that sufficient stability can be ensured even in 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. The hydrogen pressure in step 1 above can be carried out at about 50 bar or less in terms of reaction safety and economy. In terms of reaction efficiency, the hydrogen pressure may be about 1 bar or more.

The reaction of step 1 can be carried out under a temperature condition of about 0 to 60 ° C, or about 10 to 50 ° C, or a room temperature (23 ° C) to about 40 ° C in a much milder process than the conventional process. 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 at least about 1 hour in terms of reaction efficiency, and may be about 96 hours or less in terms of reaction selectivity and economical efficiency.

The method for preparing a tetrahydroindene derivative of the present invention further includes a step of reacting a compound of the formula (a) with an alkyl lithium and then reacting the compound with a compound containing a Group 4 transition metal to generate the compound of the formula .

(A)

Wherein R ₁ , R ₂ , and R ₃ are as described above.

Herein, the compound represented by the above formula (a) is an indene compound and has stable characteristics at room temperature and air. For example, the indene compound is selected from the group consisting of indene, 3-butyl-1H-indene, 2-methyl-1H-indene, 2-methyl-4-phenyl-1H-indene.

Further, the compound containing the Group 4 transition metal has a characteristic of being vulnerable to moisture. Examples of the Group 4 transition metal include Zr, Ti, Hf, and the like. The transition metal of the Group 4 transition metal compound is preferably TiCl ₄ , ZrCl ₄ , HfCl ₄ , and the like. On the other hand, the transition metal compound may be in a form containing Ta, V, Nb, Sc, Y, etc. in addition to a transition metal of Group 4.

The above-described complex-compound-forming step can be carried out under moisture-free conditions, and can be carried out under inert gas conditions such as nitrogen or argon from the viewpoint of reaction stability. For example, the compound of formula (1) can be produced through a reaction represented by the following reaction formula (1).

[Reaction Scheme 1]

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

The compound of formula (a) may be prepared by any method or reaction known in the art, and various methods may be applied without particular limitation.

Hydrogenated Bis ( Indeny ) Hydrolysis of the complex (step 2)

The step 2 is a step of reacting the compound of the formula (2) generated through the hydrogen reaction of the step 1 under an alkaline aqueous solution to prepare a tetrahydroindene derivative.

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

(2)

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

The compound of formula (2) may be reacted under an aqueous alkaline solution to produce a compound of formula (3).

(3)

Wherein R ₁ , R ₂ , and R ₃ are as described above in Step 1.

The compound represented by the above formula (3) is a tetrahydroindene derivative and has stable characteristics at room temperature. Preferably, the tetrahydroidene derivative may be one of the following structural formulas.

,

,

,

,

,

,

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

Also, the aqueous alkaline solution may have a pH of about 7-14, or about 8-12, or about 9-10. 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.

The reaction temperature in step 2 may be about 0 to 60 ° C, or about 10 to 40 ° C, or about room temperature (23 ° C) to about 30 ° C. The reaction temperature of step 2 is preferably at least about 0 ° C 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 economical efficiency.

The reaction pressure of step 2 can be applied within the ordinary range known in the art, and can be performed in the atmospheric pressure range without particular limitation.

As described above, the production method according to the present invention is characterized in that the bis (indenyl) complex bis (indenyl) complex is hydrolyzed under a low hydrogen pressure and then subjected to a hydrolysis reaction under an alkaline aqueous solution, Tetrahydroindene derivatives into which various substituents have been introduced through a reaction under mild conditions than the conditions can be easily prepared and can be usefully used for mass synthesis in high yield in a safe and efficient process condition .

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Example  One

(Step 1)

Bis (indenyl) ZrCl ₂ (about 3.9 g, about 6.9 mmol), dichloromethane (DCM, about 40 mL) and PtO ₂ (about 5 mol%) were charged to a 100 mL Parr reactor. The inside was filled with H _{2 of} about 34 bar and stirred at room temperature for about 24 hours. The reaction mixture was filtered through a glass filter and the filtrate was vacuum dried to obtain bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a white powder (about 2.6 g, about 5.6 mmol, 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, d), 6.27 (2H, t).

(Step 2)

(2 g, 5.0 mmol), Toluene (about 40 mL), and a saturated aqueous NaHCO ₃ solution (about 20 mL) were added to 100 mL round bottom flask and stirred at room temperature for about 20 hours. The organic layer was separated, to remove water with MgSO _4. The solvent was evaporated 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)

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

(Step 2)

(69 g, 170 mmol), Toluene (about 1.5 L) and a saturated aqueous solution of NaHCO ₃ (about 0.75 L) were added to a solution of 5 (5,6,7-tetrahydro-1-indenyl) zirconium dichloride L reactor and stirred at room temperature for about 20 hours at a rate of about 200 rpm. The organic layer was separated, to remove water with MgSO _4. The solvent was evaporated under reduced pressure to give 33 g (280 mmol, 80% yield) of [3a], 5,6,7-tetrahydro-4H-indene in the form of a colorless liquid.

Example  3

(Step 1)

To a 100 mL Parr reactor was added bis (3-butyl-1H-inden-1-yl) zirconium (IV) chloride (2.9 g, 5.8 mmol), dichloromethane (DCM, 50 mL) and PtO ₂ Respectively. The inside was filled with H ₂ 20 bar and stirred at room temperature for 24 hours. The reaction was filtered through a glass filter and the filtrate was dried in vacuo to give the title compound as a light green solid in the form of bis (3-butyl-4,5,6,7-tetrahydro-1H-inden-1-yl) zirconium (2.5 g, 4.9 mmol, 84% yield, racemic, 1: 1 mixture of meso isomers).

^{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)

(2.5 g, 4.9 mmol), Toluene (40 mL), NaHCO 3 (4 g), and the like were added to the solution of bis (3-butyl-4,5,6,7-tetrahydro- ₃ saturated aqueous solution (20 mL) was added to a 100 mL round bottom flask and stirred at room temperature for 20 hours. The organic layer was separated, to remove water with MgSO _4. The solvent was evaporated under reduced pressure to obtain a pale yellow liquid form of 3-butyl-3a, 5,6,7-tetrahydro-4H-indene (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 ppm (s, 1 H)

Example  4

(Step 1)

To a 100 mL Parr reactor was added bis (4- (4- tert -butyl) phenyl) -2-methyl-1H-inden-1-yl) zirconium (IV) chloride (10 g, 15 mmol), dichloromethane , 40 mL) and PtO ₂ (5 mol%). The inside was filled with H ₂ 20 bar and stirred at room temperature for 24 hours. The reaction was filtered through a glass filter and the filtrate was dried in vacuo to give an intermediate, bis (4- (tert-butyl) phenyl) -2-methyl-4,5,6,7-tetrahydro-1H -inden-1-yl) zirconium (IV) chloride (8.0 g, 12 mmol, 1: 1 mixture of 79% yield, racemic, 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) 2H), 5.41 (s, 1H), 5.58 (s, 1H), 5.60 (s, 1H), 2.36-2.56 (q, 2H), 2.89-3.17 (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)

The resulting bis (4- (4- tert -butyl) phenyl) -2-methyl-4,5,6,7-tetrahydro-1H-inden-1-yl) zirconium (IV) chloride g, 12 mmol), Toluene (40 mL) and saturated aqueous NaHCO ₃ (20 mL) were added to a 100 mL round bottom flask and stirred at room temperature for 20 hours. The organic layer was separated, to remove water with MgSO _4. The solvent was evaporated under reduced pressure to obtain 7- (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) , ≪ / RTI > 7.12 (d, 2H), 7.29 (d, 2H)

Comparative Example  One

Example 1 In, the Bis (indenyl) ZrCl ₂ reaction product of step 1 The reaction was carried out in the same manner as in Example 1, except that (1H-inden-1-yl) lithium was used and NH ₄ Cl was used instead of NaHCO ₃ in Step 2 to give [3a] 5,6,7-tetrahydro-4H-indene, but the synthesis yield was poor (0.58 g, 4.8 mmol, 48% yield).

Claims (14)

Reacting a compound of formula (1) with hydrogen in the presence of a catalyst comprising a transition metal of group 8 to group 10 to form a compound of formula (2) (step 1); And
Comprising the step of reacting a compound of formula (2) below under an aqueous alkaline solution to form a compound of formula (3) (step 2).
Preparation of tetrahydroindene derivatives:
[Chemical Formula 1]

(2)

(3)

Wherein,
R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'are the same or different and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms And a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms,
M is a Group 4 transition metal,
Q ₁ and Q ₂ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyl oxyhydrocarbyl 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 method according to claim 1,
Each of R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'represents hydrogen, a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms or a linear, branched 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 an alkoxyalkyl group having 2 to 20 carbon atoms or an alkylalkoxy group having 2 to 20 carbon atoms,
Gt;
The method according to claim 1,
Wherein R ₁ , R ₂ , R ₃ , R ₁ ', R ₂ ' and R ₃ 'are each hydrogen, methyl, n-butyl, phenyl or p-
Wherein M is Zr, Hf or Ti,
Wherein Q ₁ and Q ₂ are each independently halogen, methyl, ethyl, n-butyl or t-butoxyhexyl,
Gt;
The method according to claim 1,
Wherein the transition metal of Group 8 to Group 10 is Pd, Ru, Rh, or Pt,
Gt;
The method according to claim 1,
Wherein the alkaline aqueous solution comprises _{NaOH, NaHCO 3, KOH, Na} 2 CO 3, K 2 CO 3, CaCO 3, or K ₂ PO _4,
Gt;
The method according to claim 1,
The alkaline aqueous solution has a pH of 7 to 14,
Gt;
The method according to claim 1,
The amount of the transition metal catalyst to be added is 0.1 to 50 mol%
Gt;
The method according to claim 1,
Wherein the hydrogen pressure in step 1 is 50 bar or less,
Gt;
The method according to claim 1,
Wherein the reaction temperature in step 1 is 0 to < RTI ID = 0.0 > 60 C,
Gt;
The method according to claim 1,
Wherein the reaction time of step 1 is 1 to 96 hours,
Gt;
The method according to claim 1,
Wherein the reaction temperature in step 2 is 0 to < RTI ID = 0.0 > 60 C,
Gt;
The method according to claim 1,
Wherein the reaction time of step 2 is 1 to 24 hours,
Gt;
The method according to claim 1,
Reacting a compound of formula (a) with an alkyl lithium followed by reaction with a compound comprising a Group 4 transition metal to yield a compound of formula (1)
Manufacturing method:
(A)

Wherein R ₁ , R ₂ and R ₃ are the same or different 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 And a hydrocarbyl group.
The method according to claim 1,
Wherein the tetrahydroindene derivative is one of the following structural formulas:
Gt;

,

,

,