Method for producing silafluorene derivatives

Abstract

To provide a manufacturing method by which dehydrogenation reaction under wider conditions can be carried out when a silafluorene derivative is manufactured by subjecting 2-hydrosilyl biphenyls to dehydrogenation in the presence of a rhodium compound.SOLUTION: Extensive studies have been made by the inventors, and it is found that the above problem can be solved by using bis[2-(diphenylphosphino)phenyl]ether and / or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) as a pre-ligand together with a rhodium compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an improved method for preparing silafluorene derivatives. [Background technology]

[0002] Silafluorene derivatives, which have a structure in which aromatic rings are bridged with silicon, are known as compounds that are suitable for use as raw materials for various organic semiconductors including organic electroluminescence (OLED).

[0003] As a method for producing a silafluorene derivative having a structure in which aromatic rings are bridged with silicon, for example, a method is known in which 2-hydrosilylbiphenyls are subjected to a dehydrogenation reaction in the presence of a catalyst made of a metal compound such as rhodium (e.g., Patent Document 1, Non-Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2011-184410 A [Non-patent literature]

[0005] [Non-Patent Document 1] J.Am.Chem.Soc. 2010, 132, 14324-14326. [Non-Patent Document 2] Chem.Eur.J. 2017, 23, 10861-10870. Summary of the Invention [Problem to be solved by the invention]

[0006] When the inventors of the present application re-examined the above-mentioned known production methods, they found that the reaction rate may be very slow or the reaction may stop midway depending on the reaction conditions, such as the reaction temperature, the amount of catalyst used, the solvent used in combination, and the structure of the raw material 2-hydrosilylbiphenyls (silyl compounds represented by the following general formula (1)).

[0007] An object of the present invention is to provide a novel method for producing a silafluorene derivative, which enables a dehydrogenation reaction to be carried out under a wider range of conditions than the above-mentioned known methods. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by using a specific compound (bis[2-(diphenylphosphino)phenyl]ether and / or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) as a preligand in a dehydrogenation reaction using a rhodium compound. Specifically, the present invention includes the following inventions.

[0009] [1] In the presence of a rhodium compound, bis[2-(diphenylphosphino)phenyl]ether and / or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, a compound represented by the following general formula (1):

[0010] [ka] (In the formula, R 1 and R 2 are the same or different and represent an alkyl group having 1 to 4 carbon atoms or a phenyl group. 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24are each the same or different and each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted arylalkyl group, an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an alkyl R represents a silyl group, an arylcarbonyloxy group, an amino group which may be protected, an alkylamino group, an arylamino group, an ammonium group, an alkylammonium group, an arylammonium group, a thiol group which may be protected, an alkylthio group, an arylthio group, a sulfinic acid group or a salt thereof which may be protected, an alkylsulfinyl group, an arylsulfinyl group, a sulfonic acid group or a salt thereof which may be protected, an alkylsulfonyl group, an arylsulfonyl group, an alkylazo group, an arylazo group, a phosphoric acid group or a salt thereof which may be protected, a phosphorous acid group or a salt thereof which may be protected, a cyano group, a nitro group, or an azide group. 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 may be bonded to each other to form a ring which may have a substituent. A silyl compound represented by the following general formula (2):

[0011] [ka] (In the formula, R 1 , R 2 , R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R24 is as above.) A method for producing a silafluorene derivative represented by the formula:

[0012] [2] The method for producing a silafluorene derivative according to [1], wherein the rhodium compound is a complex.

[0013] [3] The method for producing a silafluorene derivative according to [1] or [2], wherein the rhodium compound is at least one selected from the group consisting of an ethylene complex, a cyclooctene complex, a cyclooctadiene complex, and a norbornadiene complex. Effect of the Invention

[0014] According to the production method of the present invention, the amount of rhodium compound used can be reduced compared to known production methods, and the dehydrogenation reaction can be carried out at a lower temperature. Therefore, compared to known production methods, the dehydrogenation reaction can be carried out more cheaply and energetically advantageously, and therefore the production method can be said to be suitable for carrying out on an industrial scale. In addition, since the reaction can be carried out under milder conditions, even when a raw material compound (a silyl compound represented by the above general formula (1)) having a substituent (e.g., Br atom, etc.) that may be partially or completely eliminated during the reaction is used, the dehydrogenation reaction can be carried out without eliminating the substituent, and it becomes possible to produce silafluorene derivatives having a wider range of structures.

[0015] In addition, in the known production method, dioxane is considered to be suitable as a solvent (for example, Non-Patent Document 2), but dioxane is highly toxic and tends to be avoided, especially when carried out on an industrial scale. On the other hand, in the known production method, as shown in the Examples section below, when dioxane is replaced with a solvent commonly used in organic synthesis such as toluene, problems such as the reaction stopping midway or the need for more rhodium compounds can occur depending on the structure of the raw material compound (the silyl compound represented by the above general formula (1)). However, according to the production method of the present invention, even if a solvent commonly used in organic synthesis is used, the reaction proceeds in the same way as when dioxane is used, so in this respect it can be said that this production method is particularly suitable for carrying out on an industrial scale. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." In addition, in this specification, when a numerical range is shown as "A to B," it means A or more and B or less.

[0017] In the silyl compound represented by the above general formula (1) and the silafluorene derivative represented by the above general formula (2), 1 and R 2 are the same or different and represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Among the alkyl groups or phenyl groups having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferred from the viewpoint of ease of production of the silyl compound represented by the above general formula (1), and R 1 and R 2 are preferably the same substituents.

[0018] In the silyl compound represented by the above general formula (1) and the silafluorene derivative represented by the above general formula (2), 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are each the same or different and each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted arylalkyl group, an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an alkyl ... R is an optionally protected aryl group, an arylcarbonyloxy group, an optionally protected amino group, an alkylamino group, an arylamino group, an ammonium group, an alkylammonium group, an arylammonium group, an optionally protected thiol group, an alkylthio group, an arylthio group, an optionally protected sulfinic acid group or a salt thereof, an alkylsulfinyl group, an arylsulfinyl group, an optionally protected sulfonic acid group or a salt thereof, an alkylsulfonyl group, an arylsulfonyl group, an alkylazo group, an arylazo group, an optionally protected phosphoric acid group or a salt thereof, an optionally protected phosphorous acid group or a salt thereof, a cyano group, a nitro group, or an azide group. 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 may be bonded to each other to form a ring which may have a substituent, and preferably, adjacent two of them are bonded to each other to form a ring which may have a substituent, or R 14 and R 24 may be bonded to each other to form a ring which may have a substituent.

[0019] R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 When the two are bonded to each other to form a ring which may have a substituent, examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkenyl group which may have a substituent, an arylalkynyl group which may have a substituent, and a cycloalkyl group which may have a substituent.

[0020] Examples of halogen atoms in the present invention include fluorine atoms, chlorine atoms, and bromine atoms. Examples of alkyl groups which may have a substituent include lower alkyl groups (e.g., alkyl groups having 1 to 4 carbon atoms), and alkyl groups having 1 to 20 carbon atoms which may have a substituent such as the halogen atom, hydroxyl group, nitro group, and alkoxy group. Examples of alkenyl groups which may have a substituent include lower alkyl groups (e.g., alkyl groups having 1 to 4 carbon atoms), and alkenyl groups having a total of 1 to 20 carbon atoms which may have a substituent such as the halogen atom, hydroxyl group, nitro group, and alkoxy group. Examples of alkynyl groups which may have a substituent include lower alkyl groups (e.g., alkyl groups having 1 to 4 carbon atoms), and alkynyl groups having a total of 1 to 20 carbon atoms which may have a substituent such as the halogen atom, hydroxyl group, nitro group, and alkoxy group. Examples of aryl groups which may have a substituent include lower alkyl groups (e.g., alkyl groups having 1 to 4 carbon atoms), and phenyl or naphthyl groups having a total of 6 to 20 carbon atoms which may have a substituent such as the halogen atom, hydroxyl group, nitro group, and alkoxy group. Examples of the arylalkyl group which may have a substituent include a lower alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms), a phenylalkyl group or a naphthylalkyl group having a total of 7 to 20 carbon atoms which may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, or an alkoxy group. Examples of the arylalkenyl group which may have a substituent include a lower alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms), a phenylalkenyl group or a naphthylalkenyl group having a total of 7 to 20 carbon atoms which may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, or an alkoxy group. Examples of the arylalkynyl group which may have a substituent include a lower alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms), a phenylalkynyl group or a naphthylalkynyl group having a total of 7 to 20 carbon atoms which may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, or an alkoxy group. Examples of the cycloalkyl group which may have a substituent include a lower alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms), or a cycloalkyl group having a total of 6 to 20 carbon atoms which may have a substituent such as a halogen atom, a hydroxyl group, a nitro group, or an alkoxy group.Examples of the heterocyclic group which may have a substituent include a furanyl group, a thiophenyl group, a pyrrolyl group, a 2H-pyrrolyl group, a 2-pyrrolinyl group, a pyrrolidinyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, an imidazolidinyl group, an imidazolidyl group, a pyrazolyl group, a pyridyl group, a piperidinyl group, a 4H-1,4-oxazinyl group, a morpholinyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and the like which may have a substituent having a total of 4 to 20 carbon atoms.

[0021] The above R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 Among the above embodiments, hydrogen atoms, halogen atoms, optionally substituted alkyl groups, optionally substituted aryl groups, optionally substituted arylalkyl groups, and R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 Two adjacent ones of these may be bonded to each other to form a ring which may have a substituent, or R 14 and R 24 and bond to each other to form a ring which may have a substituent (wherein the substituent is a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an arylalkyl group which may have a substituent).

[0022] The rhodium compound in the present invention includes metal salts of rhodium such as rhodium chloride, dodecacarbonyltetrarhodium (Rh4(CO) 12), organic rhodium compounds such as rhodium carbonyl chloride ([RhCl(CO)2]2), and rhodium acetate complexes ([Rh(OAc)2]2), chlorotris(triphenylphosphine)rhodium (RhCl(PPh3)3), carbonylchlorobis(triphenylphosphine)rhodium (RhCl(CO)(PPh3)2), rhodium cyclooctadiene complexes ([RhCl(cod)]2), rhodium ethylene complexes ([RhCl(C2H4)2]2), rhodium cyclooctene complexes, and rhodium norbornadiene complexes are examples of rhodium compounds, and among these rhodium compounds, rhodium complexes are preferred, and in particular, ethylene complexes, cyclooctene complexes, cyclooctadiene complexes, and norbornadiene complexes are preferred.

[0023] The amount of the rhodium compound used is, for example, 0.01 mol% or more, preferably 0.05 mol% or more, relative to 1 mol of the silyl compound represented by the general formula (1). Although the reaction proceeds even if an excessive amount of the rhodium compound is used, from the viewpoint of producing the silafluorene derivative represented by the general formula (2) in an industrially advantageous manner, the upper limit of the amount used is, for example, 50 mol% or less, preferably 20 mol% or less.

[0024] In the present invention, bis[2-(diphenylphosphino)phenyl]ether (a compound represented by the following formula (3)) and / or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (a compound represented by the following formula (4)) (hereinafter, these may be collectively referred to as "preligand compounds") are used together with the rhodium compound as a preligand. By using a preligand compound in combination, the reaction proceeds more gently and with a smaller amount of catalyst than in the above-mentioned known production method, and the generation of by-products (for example, compounds in which substituents are eliminated from the target silafluorene derivative) can be suppressed, and as shown in the Examples section below, it is possible to proceed with the reaction even for compounds for which the reaction stops midway in the method described in the cited invention.

[0025] [ka] (In the above formulas (3) and (4), Ph represents a phenyl group.)

[0026] The amount of the preligand compound used is, for example, 0.5 to 5 mol, preferably 1 to 3 mol, per mol of the rhodium compound.

[0027] The present invention may be carried out in the presence of an organic solvent. Examples of organic solvents that can be used include hydrocarbons, ethers, esters, ketones, and alcohols. Examples of hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, hebutane, chloroform, dichloroethane, and trichloroethane, and aromatic hydrocarbons such as toluene, xylene, chlorobenzene, and dichlorobenzene. Examples of ethers include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Examples of esters include ethyl acetate, propyl acetate, and ethylene diacetate. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Examples of alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and benzyl alcohol. Among these organic solvents, hydrocarbons are preferred, and aromatic hydrocarbons are more preferred.

[0028] The amount of the organic solvent used is, for example, 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, and more preferably 0.5 to 10 parts by weight, per part by weight of the silyl compound represented by the general formula (1).

[0029] When carrying out the present invention, a hydrogen trapping agent may be used in combination as necessary, but it is possible to obtain a sufficient reaction rate without using a hydrogen trapping agent in combination. Examples of hydrogen trapping agents that can be used in the present invention include olefins, more specifically, ethylene, propylene, 1-butene, isobutylene, 1-pentene, 3,3-dimethyl-1-butene, 1-hexene, styrene, α-methylstyrene, 2-butene, 2-pentene, 3-methyl-2-butene, 2-norbornene, etc. When using a hydrogen trapping agent, the amount used is, for example, 0.5 to 20 moles, preferably 1 to 10 moles, more preferably 2 to 6 moles, relative to 1 mole of the silyl compound represented by general formula (1).

[0030] The temperature when carrying out the present invention is, for example, 20 to 200° C., preferably 40 to 150° C., and more preferably 40 to 120° C. In the present invention, the reaction can be carried out at a lower temperature than in the above-mentioned known production methods, and the reaction temperature can be appropriately adjusted according to the raw material compound. Therefore, a silyl compound represented by general formula (1) having a substituent that is easily eliminated during the reaction can be used as a raw material, and therefore, silafluorene derivatives having a wider range of structures can be produced.

[0031] After carrying out the present invention, the reaction mixture obtained may be subjected to a post-treatment such as a catalyst removal operation (e.g., filtration, etc.), water washing, adsorption treatment, or a combination of these, if necessary. In addition, the silafluorene derivative represented by the above general formula (2) may be separated by a conventional separation means such as extraction, concentration, crystallization, filtration, column chromatography, or a combination of these. EXAMPLES

[0032] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The yields and production rates in the examples were determined by gas chromatography (GC) (internal standard method (measurement condition 1) or area percentage value (measurement condition 2)) unless otherwise specified.

[0033] (1) Gas chromatograph (GC) measurement conditions 1 Equipment: Shimadzu GC-2014, Column: Glass column (outer diameter 5 mm, inner diameter 3.2 mm, length 2.1 m), packing material 5% OV-17 on Uniport HP, Temperature rise: 80℃→15℃ / min→280℃ (10 min hold) Inj temperature: 280℃, Det temperature: 280℃, Carrier: Nitrogen 20ml / min, Internal standard substance: Dodecane

[0034] (2) Gas chromatograph (GC) measurement conditions 2 Equipment: Shimadzu GC-2010Plus, Column: HP-5 (0.25 μm, 0.32 mm ID × 30 m), Temperature rise: 50℃ (0 min hold) → 10℃ / min → 300℃ (5 min hold) → 10℃ / min → 320℃ (3 min hold) Inj temperature: 280℃, Det temperature: 320℃, split ratio 1:20, Carrier: Nitrogen 72.1kPa (constant)

[0035] (3)NMR measurement 1 H-NMR and 13 C-NMR was performed using a JEOL-ESC400 ( 1 H 400MHz, 13 The data was recorded using a C 100 MHz spectrometer. Each data item was recorded as follows:

[0036] Chemical shift, multiplicity (s=singlet, d=doublet, dd=doublet of doublets, t=triplet, sext=sextet, m=multiplet), coupling constant (Hz), and integration.

[0037] Example 1

[0038] [ka] (In the above formulas (1-1) and (2-1), Me represents a methyl group.)

[0039] In a nitrogen-substituted sealed reaction vessel, 1.06 g of the compound represented by the above formula (1-1), 6.1 mg of rhodium cyclooctadiene complex ([RhCl(cod)]2), (0.5 mol% relative to 1 mol of the compound represented by formula (1-1), 27 mg of bis[2-(diphenylphosphino)phenyl]ether (2 mol relative to 1 mol of the rhodium compound), 3 mL of toluene, and a magnetic stirrer were placed, and the mixture was heated to 80°C and stirred at 80°C for 18 hours. The resulting reaction mixture was analyzed by gas chromatography (measurement condition 1), and the yield (GC) of the compound represented by the above formula (2-1) was 96%. Thereafter, the reaction mixture was concentrated, and the obtained concentrate was purified by Kugelrohr distillation to obtain 0.98 g (isolation yield 90%) of the compound represented by formula (2-1).

[0040] (Examples 2 to 8) The reaction was carried out in the same manner as in Example 1, except that the amount of the rhodium compound used, the amount and type of the preligand compound used, and the reaction temperature were changed as shown in Table 1. The results (yields in the reaction mixture as determined by gas chromatography) are shown in Table 1.

[0041] [Table 1] In the table, the amount of the rhodium compound used is the amount used relative to 1 mole of the compound represented by the above formula (1-1), and the amount of the preligand compound used is the amount used relative to 1 mole of the rhodium compound. In addition, DPE Phos represents bis[2-(diphenylphosphino)phenyl]ether, and xant Phos represents 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

[0042] Example 9

[0043] [ka] (In the above formulas (1-2) and (2-2), Me represents a methyl group, and n-Bu represents a normal butyl group.)

[0044] In a glass reactor equipped with a stirrer, a heater / cooler, and a thermometer, which had been previously purged with nitrogen, 198.5 g of the compound represented by the above formula (1-2), 3.07 g of rhodium cyclooctadiene complex ([RhCl(cod)]2) (1 mol% relative to 1 mol of the compound represented by formula (1-2)), 6.64 g of bis[2-(diphenylphosphino)phenyl]ether (2 mol relative to 1 mol of the rhodium compound), and 595 mL of toluene were added, and the mixture was heated to 80°C and stirred at 80°C for 3 hours. During stirring, a portion of the reaction mixture was sampled every hour and subjected to gas chromatographic analysis (measurement condition 2) to confirm the production rate of the compound represented by formula (2-2) (the results are shown in Table 2). After stirring, the reaction mixture was cooled to 25° C., the rhodium compound was removed by filtration, and the reaction mixture was concentrated to obtain a concentrated residue. The concentrated residue was crystallized using isopropanol to obtain 175.6 g (isolation yield 81%) of the compound represented by formula (2-2). The compound represented by formula (2-2) obtained 1 H-NMR and 13 The results of C-NMR analysis were as follows:

[0045] 1 H-NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.7 Hz, 1H), 7.91 (d, J = 8.7 Hz, 1H), 7.87-7.82 (m, 2H), 7.80 (d, J = 7.8 Hz, 1H), 7.53-7.47 (m, 2H), 7.46-7.40 m, 1H), 7.28 (dd, J = 1.8, 7.8 Hz, 1H), 2.68 (t, J = 7.3 Hz, 2H), 1.71-1.62 (m, 2H), 1.42 (sext, J = 7.3 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H), 0.58 (s, 6H). 13C-NMR (100 MHz, CDCl3) δ 146.9, 145.7, 142.1, 139.2, 136.8, 136.5, 132.84, 132.81, 130.8, 130.3, 128.9, 128.3, 126.5, 125.2, 120.8, 119.7, 35.6, 33.8, 22.5, 14.0, -2.7 (2C).

[0046] Comparative Example 1 The reaction was carried out in the same manner as in Example 9, except that the preligand compound (bis[2-(diphenylphosphino)phenyl]ether) was not added, and the rhodium compound was changed to 5.75 g (1 mol% per mole of the compound represented by formula (1-2)) of chlorotris(triphenylphosphine)rhodium (RhCl(PPh3)3). During stirring at 80°C, a portion of the reaction mixture was sampled every hour and subjected to gas chromatographic analysis (measurement condition 2) to confirm the production rate of the compound represented by formula (2-2). The results are shown in Table 2.

[0047] [Table 2]

[0048] As shown in Table 2 above, according to the production method of the present invention, even when the compound represented by the above formula (1-2) is used as a raw material, the reaction is completed in about 2 hours (Example 9). On the other hand, in the case of the above-mentioned conventionally known production method, the reaction hardly proceeds and stops midway (Comparative Example 1).

Claims

1. In the presence of a rhodium compound, bis[2-(diphenylphosphino)phenyl]ether and / or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, a compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, R 1 and R 2 R may be the same or different and represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are each the same or different and each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted arylalkyl group, an optionally substituted arylalkenyl group, an optionally substituted arylalkynyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally protected hydroxyl group, an alkoxy group, an aryloxy group, an aldehyde group, an optionally protected carboxyl group or a salt thereof, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, an alkyl R represents a silyl group, an arylcarbonyloxy group, an amino group which may be protected, an alkylamino group, an arylamino group, an ammonium group, an alkylammonium group, an arylammonium group, a thiol group which may be protected, an alkylthio group, an arylthio group, a sulfinic acid group or a salt thereof which may be protected, an alkylsulfinyl group, an arylsulfinyl group, a sulfonic acid group or a salt thereof which may be protected, an alkylsulfonyl group, an arylsulfonyl group, an alkylazo group, an arylazo group, a phosphoric acid group or a salt thereof which may be protected, a phosphorous acid group or a salt thereof which may be protected, a cyano group, a nitro group, or an azide group. 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 may be bonded to each other to form a ring which may have a substituent. The silyl compound represented by the following general formula (2): 【Chemistry 2】 (In the formula, R 1 , R 2 , R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 is as above.) A method for producing a silafluorene derivative represented by the formula:

2. The method for producing a silafluorene derivative according to claim 1, wherein the rhodium compound is a complex.

3. 3. The method for producing a silafluorene derivative according to claim 1, wherein the rhodium compound is at least one selected from the group consisting of an ethylene complex, a cyclooctene complex, a cyclooctadiene complex, and a norbornadiene complex.

Images