Method for manufacturing dialkylcyclopentadiene for forming thin film

Abstract

Disclosed is a method for manufacturing dialkylcyclopentadiene for forming a thin film using distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent. The method for manufacturing dialkylcyclopentadiene according to the present invention comprises a step of manufacturing dialkylcyclopentadiene by adding distilled water, a C1-C4 alkyl group (R2)-halogen (X) compound, an alkali metal compound, and an organic solvent to a cyclopentadiene (Cp)-R1 compound containing Cp and a C1-C4 alkyl group (R1).

Description

Method for producing dialkylcyclopentadiene for forming thin films

[0001] The present invention relates to a method for producing dialkylcyclopentadiene for forming a thin film using distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent.

[0002] A variety of precursors have been used to fabricate thin films, and a variety of deposition techniques have been employed. These include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metal-organic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy).

[0003] Among these, CVD and ALD processes are mainly used because they have improved composition control, high film uniformity, and effective doping control.

[0004] Chemical vapor deposition (CVD) is a chemical process that uses precursors to form thin films on a substrate surface. In a typical CVD process, precursors are passed over the surface of a substrate (e.g., a wafer) within a low-pressure or ambient-pressure reaction chamber. The precursors react or decompose on the substrate surface, forming a thin film of the deposited material. Volatile byproducts are removed by a gas flow through the reaction chamber. Controlling the thickness of the deposited film can be difficult because it depends on many parameters, such as temperature, pressure, gas flow volume and uniformity, chemical depletion effects, and timing.

[0005] Atomic layer deposition (ALD) is also a method for depositing thin films. ALD is a surface reaction-based film growth technique that provides precise thickness control and can deposit conformal thin films of a precursor-derived material onto substrates of varying composition. In ALD, precursors separate during the reaction. A first precursor passes over the substrate surface, forming a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film on the first monolayer of film on the substrate surface. This cycle is repeated to form a film of the desired thickness.

[0006] In addition, the development of products with complex shapes such as high aspect ratios and three-dimensional structures is diversifying in the semiconductor and non-semiconductor fields, and accordingly, n-alkyl cyclopentadienes that are suitable for process temperatures in various application fields and can be used in atomic layer deposition (ALD) that can overcome high step ratios are in demand.

[0007] In these thin films, n-alkyl cyclopentadiene is used as a precursor, and it is known that the yield and / or purity of n-alkyl cyclopentadiene varies greatly depending on the reaction conditions.

[0008] Therefore, there is a need to develop a method for producing n-alkyl cyclopentadiene with improved yield and / or purity.

[0009] The purpose of the present invention is to provide a method for producing dialkylcyclopentadiene, which can be stably produced under mild conditions using distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent, in the step of producing dialkylcyclopentadiene from a Cp-R1 compound containing cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1).

[0010] In addition, a method for producing dialkylcyclopentadiene is provided, which can omit the extraction process performed when only an organic solvent is used, by producing dialkylcyclopentadiene in the presence of distilled water, KOH, and DMSO.

[0011] In addition, the purpose of the present invention is to prepare a dialkylcyclopentadiene from a Cp-R1 compound using a THF solvent, NaNH 2, The present invention provides a method for producing dialkylcyclopentadiene, which does not require the use of CH3ONa, NaH, BuLi, or NaOMe and does not generate by-products or toxic gases.

[0012] In addition, it is an object of the present invention to provide a method for producing dialkylcyclopentadiene having excellent deposition characteristics by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0013] The objectives of the present invention are not limited to those mentioned above. Other objectives and advantages of the present invention not mentioned above can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the objectives and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0014] The method for producing dialkylcyclopentadiene according to the present invention is characterized by including the step of producing dialkylcyclopentadiene by adding distilled water, a C1 to C4 alkyl group (R2)-halogen (X) compound, an alkali metal compound, and an organic solvent to a Cp-R1 compound including cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1).

[0015] Each of the above C1 to C4 alkyl group (R1) and C1 to C4 alkyl group (R2) is -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3) 2, -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2 or -C(CH3)3.

[0016] The content of the organic solvent is greater than that of distilled water, and the organic solvent may include dimethyl sulfoxide (DMSO).

[0017] The above alkali metal compound may include KOH.

[0018] The above Cp-R1 compound: C1 to C4 alkyl group (R2) - halogen (X) compound can be mixed in a molar ratio of 1:0.5 to 1.5.

[0019] The above Cp-R1 compound: alkali metal compound can be mixed in a molar ratio of 1:1.0 to 1.5.

[0020] The above alkali metal compound and organic solvent can be mixed in a weight ratio of 1:4 to 10.

[0021] The method for manufacturing a metal film according to the present invention is characterized in that deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the method for manufacturing the dialkylcyclopentadiene.

[0022] The method for producing dialkylcyclopentadiene according to the present invention has the effect of stably producing dialkylcyclopentadiene under mild conditions by using distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent in the step of producing dialkylcyclopentadiene from a Cp-R1 compound containing cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1).

[0023] In addition, by producing dialkylcyclopentadiene in the presence of distilled water, KOH, and DMSO, there is an effect of being able to omit the extraction process performed when only an organic solvent is used.

[0024] In addition, in the step of manufacturing dialkylcyclopentadiene from Cp-R1 compound, there is no need to use THF solvent, NaNH2, CH3ONa, NaH, BuLi, NaOMe, and there is an advantage in that by-products and toxic gases are not generated.

[0025] In addition, the method for manufacturing dialkylcyclopentadiene has excellent deposition characteristics by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0026] In addition to the effects described above, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

[0027] The above-described objects, features, and advantages will be described in detail below with reference to the accompanying drawings, so that those skilled in the art can easily practice the technical idea of ​​the present invention. In describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, a detailed description thereof will be omitted. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to indicate the same or similar components.

[0028] Hereinafter, the phrase "any configuration is placed on (or below)" a component or "on (or below)" a component may mean that any configuration is placed in contact with the upper surface (or lower surface) of said component, and that other configurations may be interposed between said component and any configuration placed on (or below) said component.

[0029] Additionally, when it is described that a component is "connected," "coupled," or "connected" to another component, it should be understood that the components may be directly connected or connected to one another, but that other components may also be "interposed" between the components, or that each component may be "connected," "coupled," or "connected" through another component.

[0030] Hereinafter, a method for producing dialkylcyclopentadiene for forming a thin film according to some embodiments of the present invention will be described.

[0031] The inventors of the present invention have confirmed that a dialkylcyclopentadiene for thin film formation can be stably produced using distilled water.

[0032] In addition, the inventors of the present invention confirmed through experiments that in the step of producing dialkylcyclopentadiene from a Cp-R1 compound, the reaction can be carried out using distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent, and that the extraction process performed when only an organic solvent is used can be omitted. In addition, the use of THF solvent, NaNH2, CH3ONa, NaH, BuLi, and NaOMe is unnecessary, and it was confirmed that dialkylcyclopentadiene with excellent deposition characteristics can be produced by chemical vapor deposition (CVD) or atomic layer deposition (ALD) without generating byproducts and toxic gases.

[0033] The dialkylcyclopentadiene produced in the present invention has excellent heat resistance and volatility along with deposition characteristics, has high yield and high purity, and can exhibit performance required for the production of next-generation devices such as semiconductors, and thus has advantageous advantages in producing thin films.

[0034] The dialkylcyclopentadiene of the present invention is produced according to the production method of the present invention, and refers to a dialkylcyclopentadiene compound that can be used to produce a thin film by a vapor deposition process such as ALD or CVD. The dialkylcyclopentadiene can be deposited, adsorbed, decomposed, transferred, or / and passed through a substrate or its surface to produce a thin film.

[0035] The term "cyclopentadiene" refers to a five-membered cyclic hydrocarbon C5H6 with a conjugated double bond within the ring, also called a cyclopentadienyl group.

[0036] The term "alkyl" (alone or in combination with another term(s)) refers to a saturated hydrocarbon chain of 1 to 4 carbon atoms, such as, but not limited to, methyl, ethyl, propyl, butyl, etc. "Dialkyl" refers to two alkyls present. Alkyl groups can be straight-chain or branched. "Alkyl group" includes all structural isomeric forms of alkyl groups.

[0037] For example, propyl includes at least one of n-propyl and isopropyl, and butyl includes at least one of n-butyl, sec-butyl, isobutyl, and tert-butyl. Furthermore, "Me" refers to methyl, "Et" refers to ethyl, "Pr" refers to propyl, "i-Pr" refers to isopropyl, "Bu" refers to butyl, "t-Bu" refers to tert-butyl, "iBu" refers to isobutyl, "Pn" refers to pentyl, and "NPn" refers to neopentyl.

[0038] The method for producing dialkylcyclopentadiene according to the present invention is characterized by including a step of producing dialkylcyclopentadiene by adding distilled water, a C1 to C4 alkyl group (R2)-halogen (X) compound, an alkali metal compound, and an organic solvent to a Cp-R1 compound including cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1).

[0039] First, a Cp-R1 compound containing cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1) can be prepared as follows.

[0040] (a) The step of preparing a Cp-R1 compound by adding a C1 to C4 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) can be performed according to synthetic formula 1.

[0041] [Synthesis Formula 1]

[0042]

[0043] Specifically, it may include a step of (a1) forming a mixture by mixing purified water and a first alkali metal compound, and a step of (a2) adding cyclopentadiene (Cp) to the mixture, and then adding a C1 to C4 alkyl group (R1)-halogen (X) compound and a first organic solvent to prepare a Cp-R1 compound.

[0044] In the present invention, dialkylcyclopentadiene can be stably synthesized using purified water instead of an organic solvent.

[0045] The first alkali metal compound may include KOH.

[0046] At this time, the purified water of (a1) and the first organic solvent of (a2) can be mixed in a weight ratio of 1:0.5 to 2, and preferably in a weight ratio of 1:1.2 to 1.6. Since the purified water and the first organic solvent satisfy a weight ratio of 1:0.5 to 2, there is an advantageous effect of stably producing a Cp-R1 compound under mild conditions.

[0047] In addition, purified water and the first alkali metal compound (B) can be mixed in a weight ratio of 1:0.1 to 0.5, and preferably in a weight ratio of 1:0.2 to 0.3. Since the purified water and the first alkali metal compound satisfy the weight ratio of 1:0.1 to 0.5, there is an advantageous effect in stably producing a Cp-R1 compound.

[0048] In addition, 10 to 40 parts by weight of cyclopentadiene (Cp) of (a2) can be mixed with 100 parts by weight of purified water of (a1), and preferably 20 to 30 parts by weight can be mixed.

[0049] In addition, in step (a2), the cyclopentadiene (Cp): C1 to C4 alkyl group (R1)-halogen (X) compound can be mixed in a molar ratio of 1:0.5 to 1.5, and preferably in a molar ratio of 1:0.8 to 1.1.

[0050] In the C1 to C4 alkyl group (R1)-halogen (X) compound, the C1 to C4 alkyl group (R1) is -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3) 2, -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2 or -C(CH3)3.

[0051] In a C1 to C4 alkyl group (R1)-halogen (X) compound, the halogen (X) may include one of Cl, Br, and I.

[0052] The first organic solvent may include dimethyl sulfoxide (DMSO).

[0053] In this way, in the step of manufacturing a Cp-R1 compound, by using purified water in an amount greater than the cyclopentadiene (Cp) content and satisfying a molar ratio of cyclopentadiene (Cp): C1 to C4 alkyl group (R1) - halogen (X) compound of 1:0.5 to 1.5, a Cp-R1 compound can be stably synthesized, and high purity and high efficiency can be secured. If an excess of cyclopentadiene is used compared to the purified water content, the yield may decrease due to unreacted cyclopentadiene remaining.

[0054] The step of forming a Cp-R1 compound by adding a C1 to C4 alkyl group (R1)-halogen (X) compound to cyclopentadiene (Cp) can be performed at 0 to room temperature (25±2)°C, and preferably, the reaction can be performed at 0 to 10°C.

[0055] In the present invention, dialkylcyclopentadiene can be prepared from a Cp-R1 compound in the presence of distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent.

[0056] Specifically, the step of preparing dialkylcyclopentadiene by adding distilled water, a C1 to C4 alkyl group (R2)-halogen (X) compound, an alkali metal compound, and an organic solvent to a Cp-R1 compound containing cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1) can be performed according to Synthetic Formula 2.

[0057] [Synthesis Formula 2]

[0058]

[0059] Cp-R1 compound: A C1 to C4 alkyl group (R2) - halogen (X) compound can be mixed in a molar ratio of 1:0.5 to 1.5, and can be mixed in a molar ratio of 1:0.9 to 1.2.

[0060] In addition, the Cp-R1 compound: alkali metal compound (B) can be mixed in a molar ratio of 1:1.0 to 1.5, and preferably in a molar ratio of 1:1.2 to 1.4.

[0061] Additionally, the alkali metal compound (B) and organic solvent can be mixed in a weight ratio of 1:4 to 10, and preferably in a weight ratio of 1:3 to 5.

[0062] By adding more organic solvent than alkali metal compound (B), the synthetic reaction can proceed more smoothly at a dilute concentration.

[0063] The alkali metal compound preferably includes KOH, and the halogen (X) may include one of Cl, Br, and I.

[0064] It is preferred that the organic solvent include dimethyl sulfoxide (DMSO).

[0065] In the present invention, in the step of reacting a dialkylcyclopentadiene from a Cp-R1 compound, the reaction is performed in the presence of distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent, thereby producing a high yield of dialkylcyclopentadiene under mild conditions, and there is an advantage in that the extraction process performed when only an organic solvent is used can be omitted.

[0066] At this time, it is preferable that the content of the organic solvent be greater than that of the distilled water, for example, the weight ratio of distilled water: organic solvent may be 1:1.1 to 1:2.0, and preferably, the weight ratio of distilled water: organic solvent may be 1:1.1 to 1:1.5.

[0067] In the C1 to C4 alkyl group (R2)-halogen (X) compound, the C1 to C4 alkyl group (R2) is -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3) 2, -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2 or -C(CH3)3.

[0068] In a C1 to C4 alkyl group (R2)-halogen (X) compound, the halogen (X) may include one of Cl, Br, and I.

[0069] The organic solvent may include dimethyl sulfoxide (DMSO).

[0070] In this way, the step of producing dialkylcyclopentadiene from Cp-R1 compound can be carried out by reacting in the presence of distilled water, KOH as an alkali metal compound, and DMSO as an organic solvent, and the dialkylcyclopentadiene can include, for example, ethylisopropylcyclopentadiene, methylisopropylcyclopentadiene, etc. The yield of such product can be 65% or more.

[0071] The method for manufacturing a metal film according to the present invention is characterized in that deposition is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the method for manufacturing the dialkylcyclopentadiene.

[0072] The uses of these thin films include those using oxide ceramics, such as high-k capacitor films for semiconductors, gate insulating films for semiconductors, ferroelectric capacitor films for semiconductors, and superconductor thin films; those using nitride ceramics, such as barrier layers for semiconductors; and those using glass, such as optical glass for optical fibers, optical waveguides, optical amplifiers, and optical switches.

[0073] The thickness of such a thin film may be 0.1 to 100 μm, preferably 1 to 50 μm, but is not limited thereto.

[0074] Hereinafter, specific examples of a method for producing dialkylcyclopentadiene for forming a thin film are examined.

[0075] [Synthesis Formula 1]

[0076]

[0077] Example 1: Method for producing ethylcyclopentadiene

[0078] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 300 g of purified water was added, then 88.3 g (1.57 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 300 g of DMSO was added. After the mixture was cooled, 80 g (1.21 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 131.9 g (1.21 mol) of bromoethane (R1-X) / 131.9 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 300 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 79.8 g (0.847 mol, yield 70%) of ethylcyclopentadiene.

[0079] 1 H-NMR (400 MHz, C6D6): δ 5.927~6.449 (m, 3H, C=CH), δ 2.636~2.782 (d, 2H, C=C-CH2), δ 2.236~2.297 (m, 2H, Cp-CH2), δ 1.014~1.102 (m, 3H, Cp-C-CH3)

[0080] Example 2: Method for producing methylcyclopentadiene

[0081] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 300 g of purified water was added, then 88.3 g (1.57 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 300 g of DMSO was added. After the mixture was cooled, 80 g (1.21 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 171.8 g (1.21 mol) of iodomethane (R1-X) / 171.8 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 300 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 71.3 g (0.89 mol, yield 74%) of methylcyclopentadiene.

[0082] 1 H-NMR (400 MHz, C6D6): δ 6.033~6.458 (m, 3H, C=CH), δ 2.900~2.991 (d, 2H, C=C-CH2), δ 2.050~2.115 (d, 3H, Cp-CH3)

[0083] Example 3: Method for preparing n-propylcyclopentadiene

[0084] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 67.09 kg of purified water was added, and 15.63 kg (278.6 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and the internal temperature of the reaction vessel was maintained at 25°C or lower. 67.09 kg of DMSO was slowly added. The mixture was cooled to maintain 0°C, and 15.9 kg (240.5 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 29.585 kg (240.5 mol) of 1-bromopropane (R1-X) / 29.585 kg of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. After the reaction was completed, 39 kg of purified water was added to separate the upper organic layer and the lower aqueous layer, and only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 22.1 kg (204.3 mol, yield 85%) of n-propylcyclopentadiene.

[0085] 1 H-NMR (400 MHz, C6D6): δ 6.45 (m, 1H, C=CH), 6.21~6.34 (m, 1H, C=CH), 5.96~6.17 (dd, 1H, C=CH), δ 2.64~2.78 (dd, 2H, C=C-CH2), δ 2.25 (m, 2H, Cp-CH2), δ 1.43~1.52 (m, 2H, C=C-CH2), δ 0.89 (m, 3H, Cp-C-CH3)

[0086] [Synthesis Formula 2]

[0087]

[0088] Example 4: Method for producing ethylisopropylcyclopentadiene

[0089] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 150 g of purified water was added, then 31 g (0.55 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 150 g of DMSO was added. After the mixture was cooled, 40 g (0.42 mol) of ethylcyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 52.3 g (0.42 mol) of 2-bromopropane (R2-X) / 52.3 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 150 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered with Celite. The filtrate was distilled under reduced pressure to obtain 59.1 g (0.327 mol, yield 77%) of ethylisopropylcyclopentadiene.

[0090] 1 H-NMR (400 MHz, C6D6): δ 5.800~6.549 (m, 2H, C=CH), δ 2.701~2.773 (t, 2H, C=C-CH2), δ 2.603 (m, 1H, Cp-CH), δ 2.251~2.284 (m, 2H, Cp-CH2), δ 0.952~1.173 (m, 6H, Cp-C-(CH3)2) (m, 3H, Cp-C-CH3)

[0091] Example 5: Method for producing methylisopropylcyclopentadiene

[0092] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 150 g of purified water was added, then 36.4 g (0.65 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 150 g of DMSO was added. After the mixture was cooled, 40 g (0.5 mol) of methylcyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 39.2 g (0.42 mol) of 2-chloropropane (R2-X) / 39.2 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 150 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 40 g (0.324 mol, yield 65%) of methylisopropylcyclopentadiene.

[0093] 1 H-NMR (400 MHz, C6D6): δ 5.788~6.521 (m, 2H, C=CH), δ 2.834~2.920 (t, 2H, C=C-CH2), δ 2.571 (m, 1H, Cp-CH), δ 1.927~2.083 (m, 3H, Cp-CH3), δ 1.107~1.190 (d, 6H, Cp-C-(CH3)2)

[0094] Example 6: Method for producing methylpropylcyclopentadiene

[0095] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 150 g of purified water was added, then 36.4 g (0.65 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 150 g of DMSO was added. After the mixture was cooled, 40 g (0.5 mol) of methylcyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 61.4 g (0.5 mol) of 1-bromopropane (R2-X) / 61.4 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 150 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered with Celite. The filtrate was distilled under reduced pressure to obtain 59 g (0.354 mol, yield 71%) of methylpropylcyclopentadiene.

[0096] 1 H-NMR (400 MHz, C6D6): δ 5.819~6.462 (m, 2H, C=CH), δ 2.809~2.947 (t, 2H, C=C-CH2), δ 2.279~2.371 (m, 2H, Cp-CH2), δ 1.930~2.090 (m, 3H, Cp-CH3), δ 1.520~1.654 (m, 2H, Cp-C-CH2), δ 0.893~1.042 (t, 3H, C-CH3)

[0097] Example 7: Method for producing diethylcyclopentadiene

[0098] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 150 g of purified water was added, then 31 g (0.55 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 150 g of DMSO was added. After the mixture was cooled, 40 g (0.42 mol) of ethylcyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 46.3 g (0.42 mol) of bromoethane (R2-X) / 46.3 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 150 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 55.2 g (0.33 mol, yield 78%) of diethylcyclopentadiene.

[0099] 1 H-NMR (400 MHz, C6D6): δ 5.998~6.070 (m, 2H, C=CH), δ 2.710~2.763 (d, 2H, C=C-CH2), δ 2.180~2.282 (m, 4H, Cp-CH2), δ 0.948~1.150 (m, 6H, Cp-C-CH3)

[0100] Example 8: Method for producing ethylmethylcyclopentadiene

[0101] In a reaction vessel capable of mechanical stirring and maintaining a low temperature, 150 g of purified water was added, then 36.4 g (0.65 mol) of KOH (B) was slowly added until the KOH was completely dissolved, and 150 g of DMSO was added. After the mixture was cooled, 40 g (0.5 mol) of methylcyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 3 hours. While maintaining the internal temperature of the mixture at 0°C or lower, a solution of 32.2 g (0.5 mol) of chloroethane (R2-X) / 32.2 g of DMSO was slowly added. After the addition was completed, the temperature was raised to 20°C, and the mixture was stirred for 5 hours to complete the reaction. 150 g of purified water was added to the reaction vessel, the organic layer and the aqueous layer were separated, and only the organic layer was collected and filtered with Celite. The filtrate was distilled under reduced pressure to obtain 43.7 g (0.4 mol, yield 81%) of ethylmethylcyclopentadiene.

[0102] 1 H-NMR (400 MHz, C6D6): δ 5.771~6.422 (m, 2H, C=CH), δ 2.701~2.745 (t, 2H, C=C-CH2), δ 2.112~2.248 (m, 2H, Cp-CH2), δ 1.800~1.914 (m, 3H, Cp-CH3), δ 0.907~1.129 (t, 3H, Cp-C-CH3)

[0103] Comparative Example 1: Method for producing diethylcyclopentadiene using THF / NaH

[0104] NaH 60% in mineral oil (46.73 g, 1.17 mol) and anhydrous THF (400 mL) were added to the reaction vessel, and the internal temperature was lowered to -15°C. Ethylcyclopentadiene (100 g, 1.06 mol) was slowly added. The internal temperature of the reaction vessel was slowly increased and stirred for 1 hour. After cooling to below -15°C again, 1-bromoethane (127.31 g, 1.17 mol) was slowly added dropwise. After the addition was completed, the temperature was slowly increased to room temperature and stirred under reflux at 60°C for 3 hours. When the stirring was completed, distilled water was added to terminate the reaction, extracted with ethyl ether, and washed several times with distilled water. The organic layer was dried over MgSO4, filtered under reduced pressure, and the solvent was completely removed. The produced liquid was fractionally distilled under reduced pressure to obtain 102 g (yield 80%) of diethylcyclopentadiene compound.

[0105] Comparative Example 2: Method for producing diethylcyclopentadiene using THF / NaNH2

[0106] NaNH2 (41.88 g, 1.07 mol) and anhydrous THF (500 mL) were added to the reaction vessel, and the internal temperature was lowered to -20°C. Ethylcyclopentadiene (100 g, 1.07 mol) was slowly added. The internal temperature of the reaction vessel was slowly increased and stirred for 17 hours. After cooling to below -20°C again, 1-bromoethane (116.98 g, 1.07 mol) was slowly added dropwise. After the addition was completed, the temperature was slowly increased to room temperature and stirred under reflux at 60°C for 17 hours. Upon completion of the stirring, the salt generated during the reaction was removed through a filtration process, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 62 g (yield 47.7%) of a colorless, transparent liquid mixture composition of diethylcyclopentadiene compound.

[0107] Comparative Example 3: Method for producing methylpropylcyclopentadiene using THF / n-BuLi

[0108] Methylcyclopentadiene (50.0 g, 0.624 mol) and anhydrous THF (400 mL) were added to the reaction vessel, and the internal temperature was lowered to -20°C. Normal butyl lithium (173.79 g, 0.624 mol) was slowly added to the reactor. The internal temperature of the reaction vessel was slowly increased, and the reactor was stirred for 4 hours. After cooling again to -20°C or lower, 1-bromopropane (67.07 g, 0.562 mol) was slowly added dropwise. After the addition was completed, the temperature was slowly increased to room temperature, and the reactor was stirred for 12 hours. When the reaction was completed, the salt produced during the reaction was removed through a filtration process, the organic layer was extracted with diethyl ether, the organic layer was dried with MgSO4, and then filtered under reduced pressure. The solvent and volatile by-products were removed by distillation under reduced pressure to obtain 28.12 g (yield 37.27%) of a colorless transparent liquid mixed composition methylpropylcyclopentadiene compound.

[0109] Comparative Example 4: Method for producing ethylcyclopentadiene using THF / NaNH2

[0110] 300 ml of THF was added to the reaction vessel, and the internal temperature was lowered to -5°C. Then, 61.2 g (1.57 mol) of NaNH2(B) was slowly added while stirring, and the mixture was stirred for 30 minutes. After cooling the mixture, 80 g (1.21 mol) of cyclopentadiene was slowly added, and the internal temperature was maintained at 10°C or lower for 12 hours. While maintaining the internal temperature of the mixture at 0°C or lower, 95 g (1.21 mol) of 2-chloropropane (R1-X) was slowly added. The reaction was completed by stirring for 2 hours. 300 g of purified water was added to the reaction vessel to quench the mixture, and the organic layer and aqueous layer were separated. Only the organic layer was collected and filtered through Celite. The filtrate was distilled under reduced pressure to obtain 90 g (0.835 mol, yield 69%) of isopropylcyclopentadiene.

[0111] 1H-NMR (400 MHz, C6D6): δ 5.927~6.449 (m, 3H, C=CH), δ 2.636~2.782 (d, 2H, C=C-CH2), δ 2.236~2.297 (m, 2H, Cp-CH2), δ 1.014~1.102 (m, 3H, Cp-C-CH3)

[0112] The method for producing dialkylcyclopentadiene for forming a thin film according to the present invention has the advantage that, compared to the comparative example, the process of using and removing THF solvent, NaNH2, and NaOMe in the subsequent step is unnecessary.

[0113] In particular, Comparative Examples 1 and 3 must be handled with care as hydrogen gas and butane gas are inevitably generated during the reaction, posing a risk of explosion during the reaction. Comparative Example 2 also inevitably generates ammonia gas as a byproduct, posing the difficulty of removing the toxic ammonia gas.

[0114] In addition, NaH and n-BuLi used in Comparative Examples 1 and 3 are highly susceptible to oxygen and moisture, making them difficult to handle during use. Specifically, there is a disadvantage in that the reaction must be performed under an inert gas atmosphere such as nitrogen.

[0115] Although the present invention has been described with reference to the drawings exemplified above, it is to be understood that the present invention is not limited to the embodiments and drawings disclosed herein, and that various modifications may be made by those skilled in the art within the scope of the technical idea of ​​the present invention. Furthermore, even if the operational effects according to the configuration of the present invention have not been explicitly described while describing the embodiments of the present invention, it is natural that the effects predictable by the corresponding configuration should also be acknowledged.

Claims

1. A method for producing dialkylcyclopentadiene, comprising the steps of: adding distilled water, a C1 to C4 alkyl group (R2)-halogen (X) compound, an alkali metal compound, and an organic solvent to a Cp-R1 compound containing cyclopentadiene (Cp) and a C1 to C4 alkyl group (R1); 2. In paragraph 1, The above C1 to C4 alkyl group (R1) and C1 to C4 alkyl group (R2) are each -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3) 2, A method for producing a dialkylcyclopentadiene having -CH2CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2 or -C(CH3)3.

3. In paragraph 1, The content of the above organic solvent is greater than that of distilled water, A method for producing dialkylcyclopentadiene, wherein the organic solvent comprises dimethyl sulfoxide (DMSO).

4. In paragraph 1, The above alkali metal compound is a method for producing dialkylcyclopentadiene containing KOH.

5. In paragraph 1, A method for producing dialkylcyclopentadiene, wherein the above Cp-R1 compound and the C1 to C4 alkyl group (R2)-halogen (X) compound are mixed in a molar ratio of 1:0.5 to 1.

5.

6. In paragraph 1, A method for producing dialkylcyclopentadiene by mixing the above Cp-R1 compound and alkali metal compound in a molar ratio of 1:1.0 to 1.

5.

7. In paragraph 1, A method for producing dialkylcyclopentadiene by mixing the above alkali metal compound and organic solvent in a weight ratio of 1:4 to 10.

8. A method for producing a metal film, the deposition of which is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD), using the method for producing dialkylcyclopentadiene according to Article 1.

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