JP2009215237A - New compound containing silicon-silicon double bond - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound useful as e.g. a raw material, an intermediate for syntheses, a steric protective group, in the organic synthetic chemistry. <P>SOLUTION: The new compound is a disilene compound having bulky substituents represented by (E)-1,2-bis(1,1,3,3,5,5,7,7,-octaethyl-1,2,3,5,6,7,-hexahydro-s-indacen-4-yl)-1,2-dibromodisilene. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel compound containing an intersilicon double bond.

In the field of organic synthetic chemistry, it is known that bulky compounds are useful as synthetic intermediates and steric protecting groups. For example, in Non-Patent Documents 1 to 5, unsaturated bonds between heavy elements such as Si = Si bonds and P = P bonds, which were conventionally thought to be nonexistent by using bulky steric protecting groups. It has been reported that the synthesis of a compound having an interelement (interelement unsaturated bond compound) was successful.
R. West, Science 1981, 214, 1343. Yoshiaki Masaaki, JACS 1981, 103, 4587. Okazaki Renji, Tokito Nobuhiro, JACS 2000, 122, 5648. Mitsuo Kira, Nature 2003, 421, 725. Akira Sekiguchi, Science 2004, 305, 1755.

  Accordingly, an object of the present invention is to provide a novel compound useful in organic synthetic chemistry.

  As a result of intensive studies to achieve the above object, the present inventors have found a cyclic compound having an inter-silicon double bond represented by the following general formula (I), and have completed the present invention. .

That is, the above object was achieved by the following means.
[1] A compound represented by the following general formula (I).
[In General Formula (I), R ^{11 to} R ²² and R ^{31 to} R ⁴² each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are Each independently represents a hydrogen atom or a halogen atom, and A ¹ and A ² each independently represent a hydrogen atom, an alkali metal atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an unsaturated hydrocarbon group. However, at least one of A ¹ and A ² represents a halogen atom. ]
[2] In the general formula ^{(I), R 11, R} 12, R 15, R 16, R 17, R 18, R 21, R 22, R 31, R 32, R 35, R 36, R 37, R ³⁸ , R ⁴¹ and R ⁴² each independently represents an alkyl group; R ¹³ , R ¹⁴ , R ¹⁹ , R ²⁰ , R ³³ , R ³⁴ , R ³⁹ and R ⁴⁰ are each a hydrogen atom; Compound.

The compound of the present invention has high chemical stability due to its robustness, and can be bound at the A ¹ part and / or A ² part in the general formula (I) (bifunctional). It can be applied to. Further, by the general formula (I) the kind of group to be introduced into R ¹¹ to R ²² and R ³¹ to R ⁴² in can control the physical properties such as solubility. Furthermore, since it can be synthesized in a large amount by a simple method, it has high versatility.

The compound of the present invention is represented by the following general formula (I). The compound represented by the general formula (I) is useful as a starting material or an intermediate in organic synthesis because either A ¹ or A ² is a highly reactive halogen atom.
Hereinafter, the details of the general formula (I) will be described.

  In the present invention, when a certain functional group may have a substituent, the kind of substituent, the number thereof, and the substitution position are not particularly limited. Specific examples of the substituent include a halogen atom (for example, a fluorine atom). , Chlorine atom, bromine atom, iodine atom, preferably bromine atom), aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl group, tolyl group, xylyl group, mesityl group, biphenylyl group) , Naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group), an alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, diphenylmethyl group, and trityl group).

In the general formula (I), R ^{11 to} R ²² and R ^{31 to} R ⁴² each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be unsubstituted or may have a substituent. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group. From the viewpoint of solubility and the like, an alkyl group is preferable. Examples of the alkyl group include linear or branched substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Butyl, n-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, benzyl, phenethyl, diphenylmethyl, trityl Can be mentioned. Among these, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and an unsubstituted alkyl group having 1 to 6 carbon atoms is more preferable. In consideration of the stability and reactivity of the compound, R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² , R ³¹ , R ³² , R ³⁵ , R ³⁶ , R ³⁷ , Preferably, R ³⁸ , R ⁴¹ and R ⁴² each independently represent an alkyl group, and R ¹³ , R ¹⁴ , R ¹⁹ , R ²⁰ , R ³³ , R ³⁴ , R ³⁹ and R ⁴⁰ each represent a hydrogen atom.

In general formula (I), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom.

  The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom.

In the organic synthesis reaction using the compound of the present invention, when the reaction proceeds at A ¹ and / or A ² , it is preferable from the viewpoint of stability that both X ¹ and X ² are hydrogen atoms. On the other hand, If the allow the reaction to proceed at X ¹ and / or X ^2, it is preferably X ¹ and / or X ² is a halogen atom.

In general formula (I), A ¹ and A ² each independently represent a hydrogen atom, an alkali metal atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an unsaturated hydrocarbon group, provided that A ¹ and At least one of A ² represents a halogen atom.
Since the compound of the present invention contains a highly reactive halogen atom in ^one of A ¹ and A ² , it is extremely useful as a raw material for synthesis in organic synthetic chemistry. Various disilene compounds can be synthesized by substituting various substituents for the A ¹ part and / or the A ² part halogen atom.

  The alkali metal atom is, for example, a lithium atom, a sodium atom or a potassium atom, and a lithium atom is preferable from the viewpoint of reactivity.

  The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. From the viewpoint of reactivity, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a bromine atom is particularly preferable.

  The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- A pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a diphenylmethyl group, and a trityl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl group, tolyl group, xylyl group, mesityl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group. And a phenyl group is preferred.

  The hetero atom contained in the heterocyclic group is not particularly limited, and examples thereof include a nitrogen atom and a sulfur atom. The heterocyclic group may be a single ring or a condensed ring, and may be substituted or unsubstituted. Specific examples include heteromonocyclic rings such as furan ring, thiophene ring, pyrrole ring, pyridine ring, silole ring, benzofuran ring, xanthene ring, benzothiophene ring, dibenzothiophene ring, indole ring, carbazole ring, quinoline ring, acridine ring , Condensed heterocyclic rings such as a phenanthroline ring, a benzosilole ring and a dibenzosilole ring.

  The unsaturated hydrocarbon group is preferably a substituted or unsubstituted unsaturated hydrocarbon group having 2 to 30 carbon atoms, such as vinyl group, allyl group, butenyl group, styryl group, butadienyl group, ethynyl group, phenyl An ethynyl group etc. can be mentioned.

  Specific examples of the compound of the present invention include compounds shown in Examples described later. Furthermore, the following compounds can also be illustrated as a specific example of the compound of this invention.

Although the synthesis method of the compound of this invention is not specifically limited, For example, the following method can be illustrated.
First, a raw material compound is synthesized by an intramolecular Friedel-Crafts reaction using a Lewis acid catalyst shown below.

[In the above, R and R ′ each independently represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. A plurality of R and R ′ may be the same or different. Y represents a hydrogen atom or a halogen atom. ]

Next, a monomer is obtained by introducing a desired atom or substituent into the compound obtained by the above reaction. For example, by brominating the compound obtained by the above reaction, a bromo compound in which one or two bromine atoms are substituted on the benzene ring can be obtained. Further, for example, a trihydrosilyl compound in which a hydrogen-substituted silyl group is substituted on the benzene ring can be synthesized by lithiation of a monobromo compound, subsequent reaction with alkoxyhydrosilanes, and subsequent reaction with a hydride reagent. Further, by brominating hydrogen on silicon in the trihydrosilyl form, a tribromosilyl form in which a bromine-substituted silyl group is substituted on the benzene ring can be obtained. In addition, dibromodisilene, which is a dimer in which a bromine atom is substituted on silicon, can be obtained by a reduction reaction of a tribromosilyl compound.
The introduction of the silyl group is preferably performed using a liquid trialkoxysilane such as triethoxysilane (Si (OEt) ₃ H) or a solid trialkoxysilane. In order to introduce a hydrogen-substituted silyl group, an alkoxy-substituted silyl group is introduced by reaction with trialkoxysilane, and then a reduction reaction using a hydride reagent such as lithium aluminum hydride is performed.

  Regarding the reaction of the above trialkoxysilane, for example, “2,4,6-Tri-tert.butylphenyl-substituierte Silane”, H. Weiss, H. Oehme, Zeitschrift fur Anorganische und Allgemeine Chemie 568, 1989, p157-164. Can be referred to. Reference can also be made to the examples described later. For example, as the trialkoxysilane, trimethoxysilane, triethoxysilane, or triphenoxysilane can be used. As the reaction solvent, ethers such as tetrahydrofuran and diethyl ether are preferred. The amount of trialkoxysilane to be used is preferably about 1: 1 to 1:10, more preferably 1: 2 to 1: 5 as a molar ratio with respect to the bromo compound as a raw material. The reaction temperature is preferably from about −100 ° C. to room temperature, and the reaction time is preferably from several hours to several days.

  Regarding the reaction of the hydride reagent, the examples described later can also be referred to. For example, as the hydride reagent, lithium aluminum hydride, diisobutylaluminum hydride, lithium triethyl boron hydride, sodium triethyl boron hydride, potassium triethyl boron hydride, or the like can be used. As the reaction solvent, ethers such as tetrahydrofuran and diethyl ether are preferred. The amount of the hydride reagent to be used is not particularly limited as long as it is sufficient to hydrogenate the alkoxy group on silicon. The reaction temperature is preferably from about −100 ° C. to room temperature, and the reaction time is preferably from several hours to several days.

  Regarding the bromination of the trihydrosilyl compound, the examples described later can also be referred to. For example, as the brominating agent, carbon tetrabromide or N-bromosuccinimide (NBS) can be used. As the reaction solvent, alkanes such as pentane, hexane and heptane, and aromatic hydrocarbons such as benzene and toluene can be used. The amount of brominating agent to be used is preferably about 1: 3 to 1: 100, more preferably 1: 4 to 1:10, as a molar ratio with respect to the trihydrosilyl compound as a raw material. The reaction temperature is preferably from room temperature to around 60 ° C., and the reaction time is preferably from several hours to several days.

  Then, the target bromine substituted disylene compound can be obtained by dimerizing the obtained tribromosilyl body by reductive condensation reaction. Dimerization can be performed by a reduction reaction using lithium naphthalenide / THF, but the reaction for dimerization is not limited to the above reaction. Further, the target bromine-substituted disilene compound can be obtained even when an equivalent amount or a catalytic amount of naphthalene is used with respect to lithium.

For the above-mentioned reduction reaction, for example "Synthesis, Structure, and Reactions of a Kinetically Stabilized Dibromodisilene", Koji Hironaka et al., The 54 th Symposium on Organometallic Chemistry, can refer to Japan, 2007, PA127, p40. Reference can also be made to the examples described later. For example, as the reducing agent, alkali metals such as lithium, sodium and potassium, lithium naphthalenide (LiNp), sodium naphthalenide (NaNp), potassium graphite (KC ₈ ) and the like can be used. As the reaction solvent, ethers such as tetrahydrofuran, diethyl ether and 1,2-dimethoxyethane, alkanes such as pentane, hexane and heptane, and aromatic hydrocarbons such as benzene and toluene can be used. The amount of the reducing agent used is preferably about 1: 2 as a molar ratio with respect to the bromo compound as a raw material. The reaction temperature is preferably from about −100 ° C. to room temperature, and the reaction time is preferably from several hours to several days.

  Thereafter, by reacting the obtained dibromodisilene with alkyllithium or aryllithium, a bromodisylene compound substituted with an alkyl group or aryl group can be obtained. The introduction of the alkyl group or aryl group can be carried out by a reaction using an alkyl lithium or aryl lithium reagent, but is not limited to the above reaction.

The above substituents introduction reaction, for example "Synthesis, Structure, and Reactions of a Kinetically Stabilized Dibromodisilene", Koji Hironaka et al., The 54 th Symposium on Organometallic Chemistry, can refer to Japan, 2007, PA127, p40. Reference can also be made to the examples described later. For example, when introducing an alkyl group, MeLi, MeMgBr, EtMgBr, n-BuLi, and when introducing an aryl group, a lithium reagent such as PhLi or PhMgCl, or a Grignard reagent can be used. As the reaction solvent, ethers such as tetrahydrofuran, diethyl ether and 1,2-dimethoxyethane, alkanes such as pentane, hexane and heptane, and aromatic hydrocarbons such as benzene and toluene can be used. The amount of the lithium reagent or Grignard reagent used is preferably about 1: 1 to 1: 2 as a molar ratio with respect to the raw material dibromodisilene. The reaction temperature is preferably from about −100 ° C. to room temperature, and the reaction time is preferably from several hours to several days.

The raw material compounds used in the above reaction can be synthesized by known methods, and some are available as commercial products. An example of the synthesis method of the raw material compound is shown below. Details thereof are described in, for example, K. Tamao, M, Kumada, et al., JACS. 1972, 94, 4374, BCSJ. 1976, 49, 1958 and the like.
[In the above, R ′ has the same meaning as described above. Y ′ represents a halogen atom (for example, a chlorine atom, a bromine atom, or an iodine atom).

  As described above, the method for synthesizing the compound of the present invention has been described by taking the method for synthesizing a compound having a bromine atom as a halogen atom as an example, but a compound into which a desired halogen atom is introduced can be obtained by appropriately changing the reagent used. Can do.

  After the synthesis reaction, isolation and purification may be performed by a known method. Whether the target compound has been obtained can be confirmed by an identification method such as NMR. The compound of the present invention may form a salt depending on the kind of atoms or groups contained in the general formula (I), and forms a hydrate or a solvate in a free state or a salt state. However, these states are also included in the scope of the present invention.

  Since the compound of the present invention has a bulky structure, it is useful as a steric protecting group in an organic synthesis reaction. Furthermore, it can also be used as a synthetic raw material or a synthetic intermediate in an organic synthetic reaction. Moreover, the compound of the present invention can be further synthesized from the compound of the present invention as a raw material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to the aspect shown in an Example.

[Example 1]
(E) -1,2-bis (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) Synthesis of 1,2-dibromodisilene (1) 4-bromo-1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s -Synthesis of indacene
According to A. Fukazawa, Y. Li, S. Yamaguchi, H. Tsuji, K. Tamao, JACS. 2007, 129, 14164., synthesis was performed by the following method.
(i) Synthesis of 1,3-bis (1-hydroxy-1-ethylpropyl) benzene

  In a 1000 mL three-necked flask equipped with a magnetic stir bar, a Dimroth condenser, and a 200 mL dropping funnel under argon atmosphere, put ground magnesium (14.62 g, 0.601 mol) and diethyl ether (50 ml) into ethyl bromide (65.60 g 0.602 mol) in diethyl ether (50 ml) was slowly added dropwise in an ice bath. The mixture was stirred overnight at room temperature, and a solution of dimethyl isophthalate (19.63 g, 0.101 mol) in diethyl ether (200 ml) was slowly added dropwise to the resulting reaction mixture in an ice bath. Stir overnight under reflux of diethyl ether. The resulting reaction mixture was hydrolyzed with dilute hydrochloric acid and extracted with diethyl ether. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was washed with hexane and dried to give the title compound as colorless crystals. Yield 18.20 g (0.0727 mol, 72% yield).

(ii) Synthesis of 1,3-bis (1-chloro-1-ethylpropyl) benzene

1,3-bis (1-hydroxy-1-ethylpropyl) benzene (15.4 g, 61.6 mmol), dichloromethane (120 ml), and chloride as dehydrating agent in a 200 ml Schlenk tube equipped with a magnetic stir bar and gas blowing tube Calcium (about 20 g) was added, and hydrogen chloride gas was blown from the blowing tube at room temperature for 1 hour. The obtained reaction mixture was filtered through a Buchner funnel lined with Celite (registered trademark) to remove insoluble matters. The solvent was distilled off under reduced pressure, and the resulting residue was dried to obtain a brown oily substance containing the title compound as a main product. The purity of the title compound in this oil was determined by ¹ H NMR. Crude yield 16.8 g (crude yield 95%).

(iii) Synthesis of 1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene (boron trichloride catalyst)

  The 1,3-bis (1-hydroxy-1-ethylpropyl) benzene (15.4 g, 61.6 mmol) synthesized in (ii) above was prepared in a 300 mL three-necked flask equipped with a magnetic stir bar under an argon atmosphere. Add bis (1-chloro-1-ethylpropyl) benzene, 2-ethyl-1-butene (10.0 g, 119.3 mmol), dichloromethane (120 mL), and at -60 ° C, catalytic amount of boron trichloride 1.0 M dichloromethane Solution (60 mL, 60 mmol) was added. The mixture was warmed to room temperature and stirred at room temperature for 5 days. The resulting reaction mixture was hydrolyzed with 1.0 M aqueous sodium hydroxide solution. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. Impurities were removed from the resulting residue using a silica gel column (silica gel 60 manufactured by Kanto Chemical Co., Ltd., particle size 40-50 μm) using hexane as a developing solvent. Hexane was distilled off, and the obtained residue was subjected to Kugelrohr distillation to obtain the title compound as colorless crystals (bp 120-160 ° C., 0.1 mmHg). Yield 10.1 g (26.3 mmol, 43% yield).

(iv) Synthesis of 4-bromo-1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene

  In a 500 mL three-necked flask equipped with a magnetic stirrer and a Dimroth condenser under an argon atmosphere, Hexahydro-s-indacene (9.65 g, 25.2 mmol) and triethyl phosphate (200 mL) were added, and bromine (20.0 mL, 390 mmol) was added at room temperature. After stirring at 70 ° C. overnight, the resulting reaction mixture was hydrolyzed with saturated aqueous sodium sulfite. The precipitated powder was collected by filtration and washed with water and ethanol. Drying under reduced pressure gave the title compound as colorless crystals. Yield 9.11 g (19.8 mmol, 78% yield).

(2) Synthesis of (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) silane

4-bromo-1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6, in a 500 ml three-necked flask equipped with a magnetic stir bar and dropping funnel under an argon atmosphere 7-Hexahydro-s-indacene (13.9 g, 30.0 mmol) and tetrahydrofuran (300 ml) were added, and a 2.6 M n-butyllithium-hexane solution (25.0 ml, 65.0 mmol) was added dropwise at -60 ° C. The mixture was warmed to −10 ° C. over 4 hours and triethoxysilane (15.5 g, 94.3 mmol) was added. After stirring overnight at room temperature, tetrahydrofuran was distilled off under reduced pressure. Hexane was added to this mixture and filtered through a glass filter spread with Celite (registered trademark) to remove insoluble matters. Volatile components were removed under reduced pressure to give a yellow oil.
In an argon atmosphere, lithium aluminum hydride (0.956 g, 25.2 mmol) and diethyl ether (100 ml) were placed in a 500 ml three-necked flask equipped with a magnetic stir bar, and the yellow oil obtained in the above reaction was dissolved in diethyl ether ( 150 ml) was added dropwise at 0 ° C. After stirring at room temperature for 30 minutes, the reaction mixture was hydrolyzed with dilute hydrochloric acid and extracted with diethyl ether. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from hexane to give the title compound as colorless crystals. Yield 9.727 g (23.6 mmol, 79% yield).

(3) Synthesis of tribromo (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) silane

(1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s in a 200 ml eggplant-type Schlenk equipped with a magnetic stir bar under an argon atmosphere -Indasen-4-yl) silane (7.46 g, 18.1 mmol), carbon tetrabromide (30.4 g, 91.7 mmol), and hexane (100 ml) were added and stirred at room temperature for 4 days. Hexane and carbon tetrabromide were distilled off under reduced pressure, hexane was added, and the mixture was filtered through a glass filter covered with Celite (registered trademark) to remove insoluble matters. The solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from hexane to obtain the title compound as colorless crystals. Yield 8.84 g (13.6 mmol, 75% yield).
¹ H NMR (CDCl ₃ , δ) 0.75 (t, J = 7.2 Hz, 12H), 0.80 (t, J = 7.2 Hz, 12H), 1.52-1.64 (m, 4H), 1.62-1.76 (m, 4H) , 1.82 (s, 4H), 2.16-2.32 (m, 4H), 2.20-2.36 (m, 4H), 6.85 (s, 1H);
¹³ C NMR (CDCl ₃ , δ) 9.0, 10.2, 33.1, 33.5, 43.9, 47.6, 54.6, 125.9, 127.9, 151.1, 155.5;
²⁹ Si NMR (CDCl ₃ , δ) -43.2.

(4) (E) -1,2-bis (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene-4 -Il) -1,2-Dibromodisilene synthesis

Tribromo (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s was added to a 100 ml Schlenk tube equipped with a magnetic stir bar under an argon atmosphere. -Indasen-4-yl) silane (1.30 g, 2.01 mmol), anhydrous tetrahydrofuran (20 ml), and lithium naphthalenide prepared from lithium (38.4 mg, 5.53 mmol), naphthalene (0.565 g, 4.41 mmol) Tetrahydrofuran solution (5 ml) was added dropwise at -90 ° C. The mixture was stirred overnight while gradually warming to room temperature. The solvent was distilled off under reduced pressure, benzene was added, and insoluble matters were removed by centrifugation. After distilling off the solvent under reduced pressure, the resulting residue was washed with a small amount of hexane to obtain the title compound as a yellow powder. Yield 0.500 g (0.511 mmol, 51%).
¹ H NMR (C ₆ D ₆ , δ) 0.86 (t, J = 6.8 Hz, 12H), 0.88 (t, J = 7.2 Hz, 12H), 1.04 (t, J = 7.2 Hz, 12H), 1.06 (t , J = 7.2 Hz, 12H), 1.52-1.74 (m, 16H), 1.89 (s, 8H), 2.18-2.28 (m, 4H), 2.40-2.60 (m, 8H), 2.70-2.84 (m, 4H ), 6.96 (s, 2H);
¹³ C NMR (C ₆ D ₆ , δ) 9.3, 9.5, 10.8, 11.4, 33.4 (2C), 33.7, 36.8, 42.1, 47.8, 54.3, 122.4, 123.9, 150.5, 155.6;
MS (FAB): m / z; 976 (M ⁺ )
The molecular structure of the obtained compound was determined by X-ray crystal structure analysis. The molecular structure obtained by X-ray crystal structure analysis is shown in FIG.

[Example 2]
(E) -1,2-bis (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) Synthesis of 1-bromo-2-phenyldisilene

(E) -1,2-bis (1,1,3,3,5,5,7,7-octaethyl-synthesized in Example 1) was placed in a 100 ml Schlenk tube equipped with a magnetic stir bar under an argon atmosphere. 1,2,3,5,6,7-Hexahydro-s-indasen-4-yl) -1,2-dibromodisilene (0.028 g, 0.29 mmol) and anhydrous THF (30 ml), 1.9 M phenyl Lithium-dibutyl ether solution (0.40 ml, 0.76 mmol) was added dropwise at -70 ° C. The mixture was stirred overnight while gradually warming to room temperature. The solvent was distilled off under reduced pressure, hexane was added, and insoluble matters were removed by centrifugation. After the solvent was distilled off under reduced pressure, the title compound was obtained as orange crystals by recrystallization from hexane. Yield 0.052 g (0.053 mmol, 18%).
¹ H NMR (C ₆ D ₆ , δ) 0.80-1.10 (t, 48H), 1.55-1.80 (m, 16H), 1.85-1.95 (d, 8H), 2.10-2.40 (m, 10H), 2.65-2.95 (m, 6H), 6.77-6.82 (m, 3H), 6.98 (s, 1H), 6.99 (s, 1H), 7.07-7.12 (m, 2H);
¹³ C NMR (C ₆ D ₆ , δ) 9.33, 9.43, 9.50, 9.53, 10.90, 11.13, 11.29, 11.34, 32.83, 33.09, 33.14, 34.06, 34.15, 34.33, 34.67, 35.61, 41.37, 41.71, 47.80, 47.88 , 54.24, 54.45, 120.09, 122.46, 123.72, 124.86, 127.24, 128.54, 134.71, 139.19, 150.28, 150.59, 155.46, 156.57.
MS (FAB): m / z; 974 (M ⁺ )

[Example 3]
(E) -1,2-bis (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-hexahydro-s-indacene-4 -Yl) -1,2-Dibromodisilene synthesis (1) Synthesis of 5-bromo-1,3-bis (1-hydroxy-1-methylethyl) benzene

In a nitrogen atmosphere, put 5-bromoisophthalic acid dimethyl ester (7.00 g, 25.6 mmol) and tetrahydrofuran (150 mL) in a 500 mL three-necked flask equipped with a magnetic stir bar, a Dimroth condenser, and a 100 mL dropping funnel. Methyl magnesium bromide 3.0 M diethyl ether solution (45 mL, 135 mmol) was slowly added dropwise. The mixture was stirred overnight at room temperature, and the resulting reaction mixture was hydrolyzed with dilute hydrochloric acid and extracted with diethyl ether. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow solid was washed with hexane and dichloromethane to give the title compound as colorless crystals. Yield 5.54 g (20.3 mmol, 79% yield). The identification results are shown below.
¹ H NMR (CDCl ₃ , δ) 1.55 (s, 12 H), 7.48 (d, J = 1.6 Hz, 2 H), 7.53 (t, J = 1.6 Hz, 1 H);
¹³ C NMR (CDCl ₃ , δ) 31.7, 72.4, 119.2, 122.3, 126.1, 151.3.

(2) Synthesis of 5-bromo-1,3-bis (1-chloro-1-methylethyl) benzene

To a 200 mL eggplant-type Schlenk tube equipped with a magnetic stir bar, 5-bromo-1,3-bis (1-hydroxy-1-methylethyl) benzene (4.09 g, 15.0 mmol) obtained in (1) above, dichloromethane (150 mL) and calcium chloride (about 10 g) as a dehydrating agent were added, and hydrogen chloride gas was blown from the blowing tube at room temperature for 1.5 hours. The obtained reaction mixture was filtered through a Guchfunner funnel lined with Celite (registered trademark) to remove insoluble matters. The solvent was distilled off under reduced pressure, and the resulting residue was dried to give the title compound as colorless crystals. Yield 4.63 g (15.0 mmol, 100% yield). The identification results are shown below.
¹ H NMR (CDCl ₃ , δ) 1.96 (s, 12 H), 7.60 (d, J = 1.8 Hz, 2 H), 7.72 (t, J = 1.8 Hz, 1 H);
¹³ C NMR (CDCl ₃ , δ) 34.2, 68.5, 121.7, 122.1, 127.9, 148.3.

(3) Synthesis of 4-bromo-1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-hexahydro-s-indacene (trichloride Boron catalyst)

Under a nitrogen atmosphere, the 5-bromo-1,3-bis (1-chloro-1-methylethyl) benzene (4.63 g, 15.0) obtained in (2) above was added to a 200 mL eggplant-type Schlenk tube equipped with a magnetic stirrer. mmol), 2-ethyl-1-butene (2.70 g, 32.1 mmol) and dichloromethane (80 mL), and at −78 ° C., a catalytic amount of a boron trichloride 1.0 M dichloromethane solution (15 mL, 15 mmol) was added. It was. After slowly raising the temperature to room temperature, the mixture was stirred at room temperature for 3 days. The resulting reaction mixture was hydrolyzed with 1.0 M aqueous sodium hydroxide solution. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained colorless solid was recrystallized from an ethanol / dichloromethane mixed solvent to give the title compound as colorless crystals. Yield 3.65 g (9.00 mmol, 60% yield). The identification results are shown below.
¹ H NMR (CDCl ₃ , δ) 0.72 (t, J = 7.6 Hz, 12 H), 1.24 (s, 12 H), 1.58-1.68 (m, 4 H), 1.87 (s, 4 H), 2.03- 2.13 (m, 4 H), 6.67 (s, 1 H);
¹³ C NMR (CDCl ₃ , δ) 9.5, 31.4, 32.1, 40.8, 50.0, 54.1, 115.8, 117.6, 143.1, 155.2.

(4) Synthesis of (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) silane

4-bromo-1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5 in a 300 ml three-necked flask equipped with a magnetic stir bar and dropping funnel under an argon atmosphere , 6,7-Hexahydro-s-indacene (10.1 g, 25.1 mmol) and tetrahydrofuran (150 ml) were added, and 2.6 M n-butyllithium-hexane solution (21.0 ml, 54.6 mmol) was added dropwise at -50 ° C. The mixture was warmed to −20 ° C. over 2 hours and triethoxysilane (12.4 g, 75.5 mmol) was added. After stirring overnight at room temperature, tetrahydrofuran was distilled off under reduced pressure. Hexane was added to this mixture and filtered through a glass filter spread with Celite (registered trademark) to remove insoluble matters. Volatile components were removed under reduced pressure to give a yellow oil.
In a 500 ml eggplant flask equipped with a magnetic stirrer under an argon atmosphere, the diethyl ether solution (50 ml) of the yellow oil obtained in the above reaction was placed, and lithium aluminum hydride (1.02 g, 26.9 mmol) and diethyl ether ( 100 ml) was added dropwise at 0 ° C. After stirring at room temperature for 1 hour, the reaction mixture was hydrolyzed with dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from hexane to give the title compound as colorless crystals. Yield 4.41 g (12.4 mmol, 49% yield). The identification results are shown below.
¹ H NMR (CDCl ₃ , δ) 0.74 (t, J = 7.3 Hz, 12H), 1.27 (s, 12H), 1.66-1.80 (m, 4H), 1.86 (s, 4H), 1.90-2.04 (m, 4H), 4.38 (s, 3H, J _Si-H = 198 Hz), 6.83 (s, 1H);
¹³ C NMR (CDCl ₃ , δ) 9.5, 32.2, 32.8, 40.4, 50.1, 53.6, 119.2, 120.0, 151.8, 153.6;
²⁹ Si NMR (CDCl ₃ , δ) -74.4.

(5) of tribromo (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-hexahydro-s-indacene-4-yl) silane Composition

In an argon atmosphere, add 200 ml eggplant-type Schlenk with a magnetic stir bar to (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7- Hexahydro-s-indasen-4-yl) silane (3.57 g, 10.0 mmol), carbon tetrabromide (16.6 g, 50.0 mmol) and hexane (50 ml) were added, and the mixture was stirred at room temperature for 3 days. Hexane and carbon tetrabromide were distilled off under reduced pressure, hexane was added, and the mixture was filtered through a glass filter covered with Celite (registered trademark) to remove insoluble matters. The solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from hexane to obtain the title compound as colorless crystals. Yield 5.20 g (8.77 mmol, 88% yield). The identification results are shown below.
¹ H NMR (CDCl ₃ , δ) 0.77 (t, J = 7.3 Hz, 12H), 1.30 (s, 12H), 1.90 (s, 4H), 2.14-2.26 (m, 4H), 2.26-2.40 (m, 4H), 7.01 (s, 1H);
¹³ C NMR (CDCl ₃ , δ) 10.2, 32.7, 32.9, 40.6, 50.7, 55.1, 122.9, 127.0, 153.9, 154.6;
²⁹ Si NMR (79 MHz, CDCl ₃ , δ) -43.3.

(6) (E) -1,2-bis (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-hexahydro-s- Synthesis of indasen-4-yl) -1,2-dibromodisilene

Tribromo (1,1,7,7-tetramethyl-3,3,5,5-tetraethyl-1,2,3,5,6,7-) was added to a 100 ml Schlenk tube equipped with a magnetic stirrer under an argon atmosphere. Hexahydro-s-indasen-4-yl) silane (1.19 g, 2.00 mmol), anhydrous tetrahydrofuran (20 ml), and lithium naphtha prepared from lithium (29.4 mg, 4.24 mmol) and naphthalene (0.538 g, 4.20 mmol) A solution of lenide in tetrahydrofuran (5 ml) was added dropwise at -90 ° C. The mixture was stirred overnight while gradually warming to room temperature. The solvent was removed under reduced pressure, toluene was added, and insolubles were removed by centrifugation. After distilling off the solvent under reduced pressure, the resulting residue was washed with a small amount of hexane to obtain the title compound as a yellow powder. Yield 0.342 g (0.395 mmol, 40%). The identification results are shown below.
¹ H NMR (C ₆ D ₆ , δ) 0.98 (t, J = 6.9 Hz, 12H), 0.98 (t, J = 6.9 Hz, 12H), 1.29 (s, 12H), 1.31 (s, 12H), 1.91 (s, 8H), 1.96-2.08 (m, 4H), 2.16-2.28 (m, 4H), 2.64-2.78 (m, 4H), 2.76-2.88 (m, 4H), 7.07 (s, 2H);
¹³ C NMR (C ₆ D ₆ , δ) 11.0, 11.2, 32.1, 32.6, 34.5, 37.3, 40.6, 49.2, 55.0, 121.5, 122.1, 153.7, 153.8;
²⁹ Si NMR (C ₆ D ₆ , δ) 73.6;
MS (FAB): m / z; 864 (M ⁺ )

  The compounds of the present invention can be used as starting materials, synthetic intermediates, steric protecting groups and the like in various organic synthesis reactions.

(E) -1,2-bis (1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro obtained by X-ray crystal structure analysis The molecular structure of -s-indasen-4-yl) -1,2-dibromodisilene is shown.

Claims (2)

A compound represented by the following general formula (I).
[In General Formula (I), R ^{11 to} R ²² and R ^{31 to} R ⁴² each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are Each independently represents a hydrogen atom or a halogen atom, and A ¹ and A ² each independently represent a hydrogen atom, an alkali metal atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group or an unsaturated hydrocarbon group. However, at least one of A ¹ and A ² represents a halogen atom. ] In the general formula ^{(I), R 11, R} 12, R 15, R 16, R 17, R 18, R 21, R 22, R 31, R 32, R 35, R 36, R 37, R 38, R ⁴¹ and R ⁴² each independently represent an alkyl ^{group, R 13, R 14, R} 19, R 20, R 33, R 34, R 39 and R ⁴⁰ a compound according to claim 1 represents a hydrogen atom.