JP2013249308A - Method for producing new n,n,n-trimethyl-1-adamantaneammonium methyl carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for easily obtaining in high yield an N,N,N-trimethyladamantaneammonium salt.SOLUTION: A method comprises: reacting a 1-halogenated adamantane and dimethylamine with each other in the presence of iodine as catalyst to obtain N,N-dimethyl-1-aminoadamantane followed by reacting the N,N-dimethyl-1-aminoadamantane and dimethyl carbonate with each other.

Description

  The present invention relates to N, N, N-trimethyl-1-adamantanammonium methyl carbonate. N, N, N-trimethyl-1-adamantanammonium methyl carbonate is a novel compound useful as a template compound for producing zeolite.

  Zeolite is produced by reacting raw materials mainly containing an aluminum source and a silicon source in an aqueous synthetic gel to form crystals. After the crystals are grown, they are dried and then subjected to a firing treatment to remove water from the pores. It is generally obtained by removing. At that time, various zeolites are designed by using a template compound in the synthetic gel.

  It is known to use an adamantane compound as a template compound for producing zeolite.

For example, zeolite SSZ-13 has been prepared using N, N, N-trimethyl-1-adamantanammonium iodide (see, for example, Patent Document 1). Various zeolites have been prepared using N, N, N-trimethyl-1-adamantanammonium iodide and the like (see, for example, Patent Document 2). Furthermore, zeolite SSZ-23 is prepared using N, N, N-trimethyl-1-adamantanammonium hydroxide or the like (see, for example, Patent Document 3).
As a method for synthesizing these adamantane compounds, for example, there is a method of obtaining N, N, N-trimethyl-1-adamantanammonium iodide by reacting 1-aminoadamantane with 3 moles of methyl iodide in the presence of tributylamine. (For example, refer to Patent Document 1 and Patent Document 2).

  In addition, a method is described in which N, N, N-trimethyl-1-adamantanammonium iodide is reacted with silver oxide in water to obtain N, N, N-trimethyl-1-adamantanammonium hydroxide ( For example, see Patent Document 2).

  Further, a method for obtaining N, N, N-trimethyl-1-adamantanammonium hydroxide by a method of ion-exchange of N, N, N-trimethyl-1-adamantanammonium iodide using an ion exchange resin is described. (For example, see Patent Document 3).

  However, in these conventional production methods, since 1-aminoadamantane as a raw material and methyl iodide used as a reaction reagent are expensive, the obtained N, N, N-trimethyl-1-adamantanammonium iodide or N, N, N It is economically disadvantageous to use trimethyl-1-adamantanammonium hydroxide as an industrial raw material for the production of zeolite.

  Therefore, an N, N, N-trimethyladamantan ammonium salt that can be easily obtained in a high yield using a simple production method has been desired as a template compound for industrially producing zeolite.

U.S. Pat. No. 4,665,110 U.S. Pat. No. 4,544,538 Japanese Patent Publication No. 06-11648

The present invention has been made in view of the above-mentioned background art, and the object thereof is N, N, N- which can be easily obtained using a simple production method as a template compound for industrially producing zeolite.
It is to provide trimethyladamantan ammonium salt.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, from N, N, -dimethyl-1-aminoadamantane and dimethyl carbonate, a novel N, N, N-trimethyl-1-adamantanammonium methyl carbonate Has been found to be able to be synthesized, and the present invention has been completed.

  That is, the present invention provides the following formula (1):

で表されるＮ，Ｎ，Ｎ−トリメチル−１−アダマンタンアンモニウムメチルカーボネートの製造方法に関する。

It is related with the manufacturing method of N, N, N-trimethyl-1-adamantanammonium methyl carbonate represented by these.

  Since the N, N, N-trimethyl-1-adamantanammonium salt represented by the above formula (1) of the present invention can be easily obtained using a simple production method, the present invention is extremely useful industrially. is there.

1 is a ¹ H-NMR spectrum diagram of N, N, N-trimethyl-1-adamantanammonium methyl carbonate obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum diagram of N, N, N-trimethyl-1-adamantanammonium methyl carbonate obtained in Example 1. FIG.

  Hereinafter, the present invention will be described in detail.

  The N, N, N-trimethyl-1-adamantanammonium methyl carbonate represented by the above formula (1) of the present invention can be synthesized, for example, by a reaction of N, N-dimethyl-1-aminoadamantane and dimethyl carbonate. it can.

  The N, N-dimethyl-1-aminoadamantane used in the above reaction can be obtained easily and inexpensively, for example, by reacting 1-halogenated adamantane with dimethylamine in the presence of iodine as a catalyst. Can do.

  The amount of dimethyl carbonate used in the above reaction is not particularly limited, but is preferably in the range of 1 to 20 moles per mole of N, N, -dimethyl-1-aminoadamantane. Preferably it is the range of 1 mol-10 mol. If it is less than 1 mol, the reaction does not proceed stoichiometrically and unreacted N, N, -dimethyl-1-aminoadamantane remains, and if it is 20 mol or more, it is disadvantageous in terms of cost.

The above-described reaction between N, N-dimethyl-1-aminoadamantane and dimethyl carbonate is carried out in the absence of solvent or in the presence of an inert solvent. Examples of the inert solvent used in the reaction include linear aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and tridecane, dimethylbutane, methylpentane, dimethylpentane, and methyl. Branched aliphatic hydrocarbons such as hexane, trimethylpentane, dimethylhexane, methylheptane, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, methylcyclohexane, methylcycloheptane, methylcyclooctane, dimethylcyclopentane, dimethylcyclohexane , Cycloaliphatic hydrocarbons such as dimethylcycloheptane, dimethylcyclooctane, ethylcyclopentane, ethylcyclohexane, ethylcycloheptane, ethylcyclooctane, dimethyl ether Linear aliphatic ethers such as diethyl ether, n-propyl ether, n-butyl ether, n-pentyl ether, n-hexyl ether, n-octyl ether, isopropyl ether, isobutyl ether, butyl methyl ether, butyl ethyl ether, Branched aliphatic ethers such as sec-butyl methyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, and mixtures such as petroleum ether, petroleum benzine, ligroin, dimethyl sulfoxide, diethyl ether, DMF, HMPA Polar solvents, methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-
Linear primary alcohols such as heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-hexadecanol, n-octadecanol 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-ethyl-1-butanol, 4-methyl-1-pentanol, 3-methyl-1-pen Tanol, 3-methyl-
1-pentanol, 2-methyl-1-pentanol, 2-methyl-3-pentanol, 2,2-dimethyl-1-propanol, 3,3-dimethyl-1-butanol, 2-ethyl-
1-butanol, 2-ethyl-1-hexanol, 5-methyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, 2,4,4-trimethyl-1-pentanol, 3,5- Dimethyl-1-hexanol, 2-propyl-1-pentanol, 2-ethyl-
Branched primary alcohols such as 1-hexanol, 3,5,5-trimethyl-1-hexanol, 3,7-dimethyl-1-octanol, 6-methyl-1-octanol, isopropanol, 2-butanol, 2- Pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol butanol, 2-undecanol, 2-dodecanol, 2-tridecanol, 2-tetradecanol, 2-hexadecanol, 2 -Octadecanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, 3-methyl-2-pentanol, 3,3-dimethyl-2-butanol, 2,2-dimethyl-3-pen Tanol, 2-methyl-3-hexanol, 2,4-dimethyl-3-pentanol, 5-methyl-2- Hexanol, 4,4-dimethyl-2-pentanol, 6-
Branched secondary alcohols such as methyl-2-heptanol, 4-methyl-3-heptanol, 2,6-dimethyl-4-heptanol, 2,6,8-trimethyl-4-nonanol, cyclohexanol, cycloheptanol Alicyclic primary alcohols such as cyclobutanol and cyclopentanol, tert-butanol, 2-methyl-2-butanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-butanol, 3-ethyl Tertiary alcohols such as -3-pentanol, 2-methyl-2-hexanol, 2,3-dimethyl-3-pentanol, 3-methyl-3-octanol, 3,7-dimethyl-3-octanol, etc. Can be mentioned. Among these, dimethyl sulfoxide, diethyl ether, THF, DMF, HMPA, methanol, ethanol, n-propanol, and 2-propanol are polar solvents that are easily available industrially and are preferable as reaction solvents. You may use these solvents individually or in mixture in arbitrary ratios. In the present invention, methanol is particularly preferred among them because of ease of handling and economy.

  In the above reaction, the amount of solvent used is not particularly limited, but is usually in the range of 0.1 g to 100 g, preferably 0.5 g to 2.0 g, per 1 g of N, N, -dimethylaminoadamantane. It is a range. When the amount of the solvent is less than 0.1 g per 1 g of N, N, -dimethylaminoadamantane, the reaction system becomes viscous and the reaction rate may be lowered. On the other hand, when the amount is 100 g or more, the reaction solution becomes diluted and the reaction rate may be lowered.

  In the above reaction, dimethyl carbonate and low-boiling point alcohol are liable to volatilize during the heating reaction. In this case, the reaction is desirably performed in a sealed container. The pressure during the reaction is not particularly limited, but a range of normal pressure to 10 MPa is sufficient.

  In said reaction, although it does not specifically limit as reaction temperature, The range of 50-300 degreeC is preferable, More preferably, it is the range of 100-200 degreeC. If the temperature is lower than 50 ° C., a sufficient reaction rate may not be obtained, and if the temperature exceeds 300 ° C., decomposition of the target product tends to occur, which is not preferable.

  In the above reaction, the target product can usually be isolated by filtering the produced quaternary salt. However, when the reaction has sufficiently progressed and the raw material N, N, -dimethyl-1-aminoadamantane does not remain, only unreacted dimethyl carbonate and the solvent are distilled off from the reaction solution obtained after the reaction. The target can be obtained directly.

  The details of the present invention will be specifically described below using examples, but the present invention should not be construed as being limited thereto. In addition, the yield of the product in a present Example was confirmed by 1H-NMR.

In the following examples, ¹ H-NMR and ¹³ C-NMR were measured using Gemini-200 manufactured by Varian.

  Moreover, the mass spectrometry by liquid chromatography used the Bruker Daltonics company make, TOF-MS, and microTOF (ion source ESI, measurement mode positive ion).

Preparation example.
In a 30 ml simple pressure vessel made of stainless steel with a stir bar, 1.0 g (4.7 mmol) of 1-bromoadamantane and 0.24 g (0.93 mmol) of iodine are placed, and the reactor is placed in a dry ice bath under a nitrogen atmosphere. In the cooled state, 9.6 g (212 mmol) of dimethylamine was cooled and collected from the cylinder through dimethylamine gas. After sealing the reactor, it was immersed in an oil bath, heated and stirred, heated to 180 ° C., and then reacted for 4 hours under the same conditions. The pressure during the reaction did not exceed 10 Mpa. After completion of the reaction, the reactor was cooled to room temperature, and the obtained slurry was neutralized and extracted by adding 48% aqueous caustic solution and dichloromethane, and the reaction mixture obtained by liquid separation was analyzed by gas chromatography (internal Standard method). As a result, the conversion of 1-bromoadamantane was 97.1%, N, N-dimethyl-1-aminoadamantane was obtained in a yield of 91.6%, and adamantane-1-ol was 1.7%. It was confirmed that 2.3% of adamantane was obtained.

Example 1.
A stainless steel 30 ml pressure vessel containing a stir bar was charged with 3.59 g (20 mmol) of N, N, -dimethyl-1-aminoadamantane, 5.40 g (60 mmol) of dimethyl carbonate, and 2.92 g of methanol. The inside was replaced with nitrogen. After sealing the reactor, it was immersed in an oil bath, heated and stirred, heated to 145 ° C., and then reacted for 10 hours under the same conditions. After completion of the reaction, the reactor was cooled to room temperature, and the resulting liquid was depressurized with an evaporator, and unreacted dimethyl carbonate and the solvent methanol were distilled off. The crystals obtained at this time were white powder crystals, and the yield was 5.30 g. The product was subjected to nuclear magnetic resonance spectrum (NMR) analysis, mass spectrum, elemental analysis, and infrared absorption spectrum (IR) analysis. The results are shown below.

NMR analysis: ¹ H-NMR (CDCl ₃ ) δ (ppm): 3.52 (s, 3H), 3.27 (s, 9H), 3.36 (s, 3H), 2.05 to 2.07 (D, 6H) 1.71 (m, 6H).

¹³ C-NMR (CDCl ₃ ) δ (ppm): 158.2, 71.6, 52.3, 47.4, 47.3, 35.1, 34.8, 30.0.

  Mass spectrometry by liquid chromatography ESI method (m / e): molecular weight of N, N, N-trimethyl-1-adamantanammonium skeleton 194.191 (M +).

Elemental analysis (measured value): C67.6, H10.3, N5.2
(Theoretical value: C66.9, H10.1, N5.2).

As a result of conducting NMR analysis of the product, it did not contain N, N, -dimethyl-1-aminoadamantane, and the conversion rate was 100%. The measurement result of ¹ H-NMR of the product is shown in FIG. 1, and the measurement result of ¹³ C-NMR is shown in FIG. Moreover, when the mass spectrum by the liquid chromatography of a product was measured, the molecular weight (M + = 194.191) of N, N, N-trimethyl-1-adamantanammonium skeleton was confirmed. These and the results of elemental analysis also supported the structure of this compound, and it was confirmed that N, N, N-trimethyl-1-adamantanammonium methyl carbonate was obtained in a yield of 98.4%.

Example 2
In a 200 ml autoclave, 17.93 g (0.1 mol) of N, N, -dimethyl-1-aminoadamantane and 90.08 g (1.0 mol) of dimethyl carbonate were placed, and the inside of the reactor was replaced with nitrogen. After sealing the reactor, the mixture was heated and stirred, the temperature was raised to 145 ° C., and the reaction was continued for 5 hours under the same conditions. At that time, the pressure during the reaction did not exceed 10 MPa. After completion of the reaction, the reactor was cooled to room temperature, and the resulting slurry was filtered under a nitrogen atmosphere to obtain white wet crystals.

  As a result of NMR analysis, this crystal did not contain N, N, -dimethyl-1-aminoadamantane, and N, N, N-trimethyl-1-adamantanammonium methyl carbonate was obtained in a yield of 59.7%. I confirmed.

Claims (4)

1-halogenated adamantane and dimethylamine are reacted in the presence of iodine as a catalyst to obtain N, N-dimethyl-1-aminoadamantane, and N, N-dimethyl-1-aminoadamantane and dimethyl carbonate A method for producing N, N, N-trimethyl-1-adamantanammonium methyl carbonate represented by the following formula (1):

The production method according to claim 1, wherein the amount of dimethyl carbonate used is in the range of 1 to 20 moles per mole of N, N, -dimethyl-1-aminoadamantane.   2. The reaction of N, N-dimethyl-1-aminoadamantane with dimethyl carbonate in the presence of a solvent in the range of 0.1 g to 100 g per 1 g of N, N, -dimethylaminoadamantane. The manufacturing method according to claim 2. The reaction of N, N-dimethyl-1-aminoadamantane and dimethyl carbonate is carried out in a sealed container, the pressure during the reaction is in the range of normal pressure to 10 MPa, and the reaction temperature is in the range of 50 to 300 ° C. The manufacturing method according to any one of claims 1 to 3, wherein:

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