WO2006001398A1 - ポリハロゲン化ジアマンタン類及びその誘導体の製造方法 - Google Patents
ポリハロゲン化ジアマンタン類及びその誘導体の製造方法 Download PDFInfo
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- WO2006001398A1 WO2006001398A1 PCT/JP2005/011678 JP2005011678W WO2006001398A1 WO 2006001398 A1 WO2006001398 A1 WO 2006001398A1 JP 2005011678 W JP2005011678 W JP 2005011678W WO 2006001398 A1 WO2006001398 A1 WO 2006001398A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/18—Polycyclic halogenated hydrocarbons
- C07C23/20—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic
- C07C23/46—Polycyclic halogenated hydrocarbons with condensed rings none of which is aromatic with more than three condensed rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/90—Ring systems containing bridged rings containing more than four rings
Definitions
- the present invention relates to a method for producing polyoctagenated diamantanes and diamantane polyols that are useful as raw materials for producing functional materials and electronic materials.
- the diamantane derivative has a similar skeleton to the adamantane derivative. Since adamantane derivatives are characterized by excellent heat resistance and high transparency, diamantane derivatives having a similar skeleton are also highly functional materials such as heat resistant polymers, and electronic materials such as resists for semiconductors that require transparency. It is expected to be used as a raw material for materials. Among the diamantane derivatives, polyhalogenated diamantanes are important compounds as starting materials for producing various diamantane derivatives.
- the resulting dibromodiamantane is 4, 9 It is a mixture of structural isomers with bromine atoms bonded to the 1st, 1st, 6th, 1st and 4th positions. Since these isomers have similar chemical and physical properties, it is difficult to separate the isomers from each other. Furthermore, in this manufacturing method, since bromine is used in large quantities, there is a problem that the manufacturing cost increases.
- Some produce 9,9-dichlorodiamantane using 9-diamantanediol do not know a report example relating to a method for producing a polychlorodiamantane starting from diamantane. Since halosulfonic acid is relatively inexpensive, its use in the production of polyhalogenated diamantane is preferred for reducing production costs. However, the present inventors do not know a report example of a production method of dihalogenated diamantanes and trichlorodiamantanes in which diamantane is used as a starting material and halosulfonic acid is reacted with the starting material.
- diamantanes are not used as a raw material in the conventional method for producing polyhalogenated diamantanes. Furthermore, conventional production methods do not provide single-structured polyhalogenated diamantanes. Therefore, in order to obtain single-structured polyhalogenated diamantanes, excessive purification or cost is required. This is not necessarily an industrially advantageous method.
- various corresponding diamantane derivatives are obtained and applied to electronic materials, etc. Each content ratio of diamantane derivatives having different substitution positions may vary every time an electronic material or the like is manufactured. In this case, the physical properties of the electronic material obtained may not always be constant.
- diamantane polyols are important compounds as starting materials for producing various diamantane derivatives.
- the method for producing diamantane polyols is a method of oxidizing diamantane using 96% sulfuric acid (Jorna 1 of the Chemical Society Perkin Transaction 1, 1 9 7 2 years, 2 6 9 1 There is. In addition, a method of reacting dibromodiamantane with 65% nitric acid to obtain diamantanediol (C o 1 lectionof C zecosolvak Chemical com nic nications, -1 9 8 3, Vol. 48, 1 1 6 p. 2) In the former method, the selectivity is low and diamantanone is generated in addition to diamantanediol. 4,9-diamandanediol produced only 5%.
- each of the above production methods is not necessarily an industrially advantageous method in that the reaction yield is low and the number of applicable polyhalogenated diamantanes is small. Therefore, a method for producing diamantane polyols at low cost and in high yield is desired. Disclosure of the invention
- the present inventors have intensively studied to solve the above problems. As a result, it was found that polyhalogenated diamantanes can be obtained with high purity and low cost by reacting diamantanes with halosulfonic acid. Furthermore, the present inventors have found that diamantane polyols can be obtained by reacting polyoctalogenated diamantanes with water in the presence of a water-soluble organic solvent and a carboxylate. . The present invention has been completed based on these findings.
- the first object of the present invention is to provide a method for producing polyhalogenated diamantanes with high purity and low cost from diamantanes as starting materials.
- the second object of the present invention is to provide a method for producing diamantane polyols at a low cost and in a high yield from the polyagitated diamantanes produced by the above method.
- the present invention is a process for producing polyhalogenated diamantanes characterized in that polyhalogenated diamantanes are obtained with high purity and low cost by mixing and reacting diamantanes and halosulfonic acid. Concentrated sulfuric acid or an inorganic salt may be added to the reaction system. Further, the halosulfonic acid may be divided into a plurality and added to the reaction system.
- the present invention provides a diamantambo by reacting polyoctalogenated diamantane with water in the presence of a water-soluble organic solvent and a carboxylate. This is a method for producing diamantane polyols for producing riols.
- polyhalogenated diamantanes can be produced from diamantanes with high purity and at low cost.
- diamantane is a compound having many cross-linking positions and bridge head positions (positions in which the carbon constituting the skeleton is a tertiary carbon in the diamantane skeleton).
- this compound is polyhalogenated, the position of substitution of the halogen differs.
- a mixture of polyhalogenated diamantanes is usually obtained.
- the production method of the present invention is extremely useful as an industrial production method for polyhalogenated diamantanes that are important as raw materials for the synthesis of various diamantane derivatives including functional polymers.
- diamantane polyols can be obtained at low cost and in high yield using the polyhalogenated diamantanes produced as described above as raw materials.
- chlorinated products are known to be less reactive but less reactive than brominated or iodinated products.
- the target product can be obtained with high yield even when polychlorodiamantanes are used as raw materials.
- the production method of the present invention is extremely useful as an industrial production method of diamantane polyols that are important as raw materials for synthesizing various diamantane derivatives including functional polymers.
- FIG. 1 shows the N M R spectrum of 4,9-dichlorodiamantane obtained in Example 5.
- FIG. 2 is the 13 C-NMR spectrum of 4,9-dichlorodiamantane obtained in Example 5.
- Figure 3 shows the results of 1, 4, 9 monotrichlorodiamantane obtained in Example 8. NMR spectrum.
- FIG. 4 is a 13 C-NMR spectrum of 1,4,9-trichlorodiamantane obtained in Example 8.
- FIG. 5 is an NMR spectrum of dibromodiamantane obtained in Comparative Example 1.
- FIG. 6 is an NMR spectrum of 4,9-diamandanediol obtained in Example 17.
- FIG. 7 is the 13 C-NMR spectrum of the 4,9-diamantandiol obtained in Example 17.
- FIG. 8 is the NMR spectrum of 1,4,9-diamantantriol obtained in Example 23.
- FIG. 9 is a 13 C-NMR spectrum of 1,4,9-diamantantriol obtained in Example 23.
- a dihalogenated diamantane is obtained by reacting diamantane with a halosulfonic acid.
- any diamantane having a diamantane skeleton can be used as the diamantane used as a raw material in the production method of the present invention.
- the diamantanes represented by are preferred in view of the importance of industrial use and availability.
- 1 ⁇ ! ⁇ 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Of these, a methyl group is particularly preferred for the above reasons.
- suitable compounds include diamantane, 1-methyldiamantane, 1-ethyldiamantane, 4-methyldiamantane, 4-ethyldiamantane, 1,4-Dimethyldiamantane, 1,4-Diethyldiamantane, 1,6-Dimethyldiamantane, 1,6-Diethyldiamantane, 4,9-Dimethyldiamantane, 4,9-Jetyldiamantane, etc. Can be mentioned.
- ⁇ rosulfonic acid is represented by the following formula (2) XS 0 3 H (2) ⁇ Wherein X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ⁇ It is a compound shown by.
- Suitable compounds among the octalosulfonic acids represented by the formula (2) include chlorosulfonic acid, promosulfonic acid, and iodine sulfonic acid. Chlorosulfonic acid is particularly preferred because it is inexpensive.
- the amount of halosulfonic acid used is preferably determined from the balance between the effect of halosulfonic acid serving as a reaction solvent and increasing the reaction rate and the ease of post-treatment after completion of the reaction.
- the amount of halosulfonic acid used is preferably 2 to 50 mol, more preferably 3 to 25 mol, and more preferably 4 to 10 moles are particularly preferred.
- the amount of halosulfonic acid used is preferably 3 to 100 mol, more preferably 4 to 50 mol, and more preferably 6 to 4 mol per 1 mol of diamantane. 0 mole is particularly preferred.
- the first dihalogenated diamantanes dissolve to some extent in halosulfonic acid, so the reaction proceeds from dihalogenation to further trihalogenation, resulting in the formation of trihalogenated diamantanes.
- concentrated sulfuric acid which is a poor solvent for dihalogenated diamantanes, coexists in the reaction system.
- dihalogenated diamantane produced by reaction of diamantane and halosulfonic acid is precipitated from the reaction solution.
- the formation of trihalogenated diamantane is suppressed.
- dihalogenated diamantanes can be produced with high selectivity.
- concentrated sulfuric acid is added to the reaction kettle in advance. This also has the advantage of preventing damage to the reaction kettle when diamantane is charged. Any method of mixing concentrated sulfuric acid may be adopted, but usually a method of adding halosulfonic acid to a suspension of diamantanes and concentrated sulfuric acid is preferred.
- the amount of concentrated sulfuric acid mixed is not particularly limited, but from the viewpoint of a large amount of target dihalogenated diamantanes and ease of post-treatment, 0.1 to 20 parts by mass are preferred, especially 0.5-1
- Concentrated sulfuric acid is not limited to the production of dihalogenated diamantanes, and may be used for the production of trihalogenated diamantanes. As described above, by adding concentrated sulfuric acid to the reaction kettle in advance, the risk of damage to the reaction kettle when diamantane is charged into the reaction kettle can be reduced. The amount used in this case is the same as in the case of the dihalogenated diamantane.
- halosulfonic acid When octarogenation reaction is performed by adding concentrated sulfuric acid to the reaction system, halosulfonic acid may be consumed without reacting with diamantane due to the reaction of water contained in concentrated sulfuric acid with halosulfonic acid. is there.
- the amount of halosulfonic acid used is the amount excluding the amount of halosulfonic acid that is decomposed by water contained in concentrated sulfuric acid.
- ⁇ Losulfonic acid can be divided into two or more fractions. Preferably, 2 to 5 fractions are divided. Furthermore, there is no restriction on the addition time interval of the halosulfonic acid fractions after the second fraction.
- the progress of the halogenation reaction can be ascertained by analysis by gas chromatography (hereinafter simply referred to as GC), and after confirming that the reaction has almost stopped, a new fraction is added. It is preferred to restart the reaction.
- GC gas chromatography
- halosulfonic acid may be divided so as to add 3 moles.
- an inorganic salt is present in the reaction system.
- inorganic salt is present in the reaction system, the purity of the resulting polyhalogenated diamantane is improved, and coloring and the like are reduced.
- Known inorganic salts can be used without limitation.
- metal chloride salts such as sodium chloride, potassium chloride, magnesium chloride and calcium chloride
- metal odorated salts such as sodium bromide, potassium bromide, magnesium bromide and calcium bromide
- Metal iodides such as potassium iodide, magnesium iodide, calcium iodide
- metal carbonates such as lithium carbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium carbonate
- lithium sulfate, sodium sulfate, magnesium sulfate, potassium sulfate And sulfates such as calcium sulfate.
- metal chloride salts and sulfates are preferable, and sodium chloride and sodium sulfate are particularly preferable because of the effect of improving the purity of the polyhalogenated diamantane obtained and reducing the coloration.
- the amount of inorganic salt added is not particularly limited, but if it is excessively large, the reaction rate will be Get smaller. If the amount is too small, the effect of adding an inorganic salt is lowered. Therefore, the addition amount of the inorganic salt is preferably from 0.01 to 50 mol, particularly preferably from 0.05 to 10 mol, based on 1 mol of the diamantane to be used.
- the reaction temperature between the diamantane and the halosulfonic acid is not particularly limited, and may be appropriately adjusted according to the desired polyhalogenated diamantane.
- the lower the reaction temperature, the lower the reaction rate, and the lower the solubility of diamantanes and the generated halogenated diamantanes in the reaction solution the smaller the number of halogen atoms introduced into the diamantanes.
- the reaction temperature is generally in the range of 0 to 100 ° C.
- the reaction temperature is preferably 0 to 60 ° C, more preferably 5 to 50 ° C.
- the reaction temperature is preferably 20 to 100 ° C, more preferably 25 to 90 ° C.
- the reaction time is not particularly limited, but usually 4 to 48 hours are preferable. With this reaction time, a sufficient conversion rate can be obtained.
- an organic solvent may be added to the reaction system.
- the organic solvent to be added those having low reactivity with halosulfonic acid or concentrated sulfuric acid can be used. Specific examples include halogenated aliphatic hydrocarbons such as methylene chloride, black mouth form, and carbon tetrachloride.
- the inside can be sufficiently replaced with an inert gas such as nitrogen beforehand and dried. Structure that can vent inert gas Those are preferred.
- the following methods can be exemplified. That is, after cooling the reaction solution to room temperature, water is added dropwise to the reaction solution while cooling the reaction solution to 30 ° C. or lower to decompose the remaining halosulfonic acid. Then, an organic solvent (dichloromethane, black form, etc.) that dissolves the polyhalogenated diamantane is added to extract the polyhalogenated diamantane. The organic layer obtained by the extraction operation is washed with an aqueous solution such as a basic aqueous solution until neutral. After confirming that the organic layer is neutral, a crude product of polyhalogenated diamantane can be obtained by concentrating the organic layer. The crude product usually contains 80% by mass or more of the desired polyhalogenated diamantane.
- the crude product can be separated from the reaction solution by filtration or centrifugation.
- the polyhalogenated diamantane crude product isolated by the post-treatment can be used as it is for various applications.
- adsorption treatment such as activated carbon treatment, sili-force treatment, and alumina treatment
- various impurities contained in the coarse body are removed to further increase the purity, and decolorization (removal of color derived from impurities) is also possible. Is done.
- a higher-purity target product can be obtained by purification by a known method such as recrystallization, sublimation purification, reslurry treatment or the like.
- the reslurry treatment is performed by adding an organic solvent that selectively dissolves impurities contained in the target polyhalogenated diamantane crude product, and then slurrying the slurry, followed by drying. This is a method for obtaining high-purity polyhalogenated diamantanes.
- the dihalogenated diamantane obtained by the above production method has three structural isomers because there are six bridgehead positions of diamantane.
- R 1 and R 3 have the same meanings as those in formula (1), and X represents a halogen atom such as fluorine, chlorine, bromine or iodine ⁇
- Examples of the 4,9-dihalogenated diamantane represented by the above formula (3) include 4,9-dichlorodiamantane, 4,9-dibromodiamantane, 4,9-jododiamantane, 1-methyl-4,9-dichlorodiamer.
- R 2 and R 4 are the same as those in formula (1), respectively.
- the 1,6-dihalogenated diamantane represented by the formula (4) includes 1,6-dichlorodiamantane, 1,6-dibromodia Mantane, 1,6-diazodiamantane, 4-methyl-1,6-dichlorodiamantane, 4-methyl-1,6-dibromodiamantane, 4-methyl-1,1, 6-Jododiamantane, 4-Ethyl-1,6-Dichlorodiamantane, 4_Ethyl1,6-Dibromodiamantane, 4-Ethyl-1,6—Jododiamantane, 4,9-dimethyl-1,6 —Dichlorodiamantane, 4,9-dimethyl—1, 6-dibromodiamantane, 4,9-one Dimethyl-1,6-jodediamantane, 4,9-jetyl-1,6-dichlorodiamantane, 4,9-dimethyl—1, 6-dibromodiamantane, 4,
- R 3 and R 4 have the same meanings as those in formula (1), and X represents a halogen atom such as fluorine, chlorine, bromine or iodine ⁇
- 1,4-dihalogenated diamantanes represented by the above formula (5) 1,4-dichlorodiamantane, 1,4-dibromodiamantane, 1,4-jododiamantane, 6-methyl-1,4-dichlorodiamantane, 6-methyl-1,1,4-dibromodiamantane, 6-methyl 1,1,4-Jodium Diamantane, 6-Ethyl-1,4-dichlorodiamantane, 6-Ethyl-1,4-Dibromodiamantane, 6-Ethyl-1,4-Jododiamantane, 9-Methyl-1, 4-Dichlorodiamantane, 9-Methyl-1,4-Dibromodiamantane, 9-Methyl-1,4-Diodediamantane, 9-Ethyl-1,4-Dichlorodiamantane, 9-Ethyl-1,4-dibromo Diamantane,
- trihalogenated diamantane When trihalogenated diamantane is produced, two types of trihalogenated diamantane are produced.
- R 3 has the same meaning as in formula (1), and X represents a halogen atom such as fluorine, chlorine, bromine, iodine ⁇
- 1,4,9 monotrihalogenated diamantane represented by the above formula (6) include 1, 4,9-trichlorodiamantane, 1, 4,
- R 4 has the same meaning as in formula (1), and X represents a halogen atom such as fluorine, chlorine, bromine or iodine ⁇
- 1,4,6-Trihalogenated diamantane represented by the following formula is obtained.
- Specific examples of the 1,4,6_trihalogenated diamantane represented by the formula (7) include 1,4,6-trichlorodiamantane, 1,4,6-tribromodiamantane, 1 , 4, 6-triiododiamantane, 9-methyl-1,4,6-trichlorodiamantane, 9-methyl-1,4,6-tribromodiamantane, 9-methyl-1,4,6-triiododiamantane, 9-ethylyl Examples include 1,4,6-trichlorodiamantane, 9-ethyl-1,4-, 6-tribromodiamantane, 9-ethyl-1,4,6-triododiamantane, and the like. Production of diamantane polyols
- the polyhalogenated diamantane produced by the method for producing polyhalogenated diamantane is reacted with water in the presence of a water-soluble organic solvent and a carboxylate.
- the polyhalogenated diamantane used as a raw material can be produced by any production method.
- water-soluble organic solvent used in the present invention a known water-soluble organic solvent that can be mixed with water at room temperature can be used without limitation.
- N, N-dimethylformamide is particularly preferred because the reaction proceeds rapidly and the price is low.
- the amount of water-soluble organic solvent used is not particularly limited, but it is preferable to determine the amount of water-soluble organic solvent based on the balance between the kettle yield and the smoothness of the reaction.
- the amount of the water-soluble organic solvent used is preferably 1 to 100 mol, and 2 to 50 mol, relative to 1 mol of the dihalogenated diamantane. More preferred.
- the amount of water-soluble organic solvent used is preferably 2 to 200 mol, more preferably 3 to L0 0 mol, per 1 mol of trihalogenated diamantane. .
- the water used for the reaction is the raw polyhalogenated diama It has the role of hydrolyzing tantalum.
- the amount to be used is preferably determined in consideration of the rapidity of the reaction and the high recovery rate.
- the polyhalogenated diamantane used is a dihalogenated diamantane
- the amount of water used is preferably 5 to 500 moles per mole of dihalogenated diamantane, and 20 to 400 moles. Is more preferable.
- the amount of water used is preferably from 5 to 100 mol, more preferably from 30 to 800 mol, per mol of the trihalogenated diamantane.
- the carboxylate has a cation bonded to the halogen atom of the polyhalogenated diamantane in its molecule.
- the carboxylate captures the hydrogen halide produced when polyhalogenated diamantanes react to form diamantane polyols.
- alkali metal formate salts such as lithium formate, sodium formate, potassium formate; alkali earth metal formate such as magnesium formate, calcium formate, barium formate; vinegar such as lithium acetate, sodium acetate, potassium acetate Acid alkali metal salts; alkaline earth metal salts of acetate such as magnesium acetate, calcium acetate and barium acetate.
- lithium acetate, sodium acetate, and potassium acetate are preferred from the standpoint of easy availability and high reactivity. Two or more of these may be used in combination.
- the amount of carboxylate used is not particularly limited, but is preferably determined based on the balance between good kettle yield and high reactivity.
- the amount of the carboxylate used is preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of the dihalogenated diamantane.
- trihalogenated diamantane force against 1 mol of trihalogenated diamantane
- the amount of rubonic acid used is preferably 3 to 15 mol, more preferably 3 to 7 mol.
- the reaction temperature is not particularly limited. However, if it is too low, the progress of the reaction is slow, and if it is too high, the operability becomes poor. Therefore, 100-200 ° C is preferable, and 120-180 ° C is more preferable.
- the reaction time is not particularly limited. Usually, sufficient conversion can be obtained in 3 to 48 hours.
- the reaction is preferably carried out under pressure in a closed system such as an autoclave.
- the reaction pressure depends on the reaction temperature, the reaction pressure is preferably 0.2 to 0.8 MPa.
- sublimable polyhalogenated diamantanes may precipitate on the upper inner wall of the autoclave where the temperature is relatively low, making it impossible to participate in the reaction.
- the refluxing water-soluble organic solvent is deposited on the upper inner wall.
- R 1 and R 3 are the same as defined in the formula (1) ⁇
- a suitable compound is specifically exemplified.
- 4,9-diamantanediol, 1-methyl-4,9_diamantanediol, 1-ethyl-4,9-diamantanediol, 1,6-dimethyl-4,9-diamantanediol, 1,6- Examples include Jetyl 4, 9 diamandanediol.
- 1,6-diamandenediol represented by the following formula (9) can be obtained.
- 1,6-diamantanediols represented by formula (9) a preferred compound is specifically exemplified.
- 1,6-diamantanediol, 4_methyl-1,6-diamantanediol, 4-ethyl-1,6-diamananediol, 4,9-dimethyl-1,6diamantanediol, 4, 9-Jetyl 1,6-diamantanediol and the like can be mentioned.
- 1,4-diamantanediol represented by the following formula (10) can be obtained.
- R 3 and R 4 have the same meanings as those in the formula (1) ⁇ , among the 1,4-diamanenediols represented by the formula (10), specific examples of suitable compounds Illustratively, 1,4-diamantanediol, 6-methyl-1,4-diamantanediol, 6-ethyl-1,4-diamantanediol, 9-methyl-1,4-diamantanediol, 9-ethyl 1,4-diamantanediol, 6,9-dimethyl-1,4-diamantanediol, 6,9-jetyl-1,4-diamantanediol, and the like.
- 1,4,9-diamantanetriol represented by the following formula (11) is obtained.
- 1,4,9-diamantantriols represented by the formula (11) specific examples of suitable compounds include 1,4,9-diamantantriol, 6-methyl-1,4,9- And diamantanetriol, 6-ethyl-1,4-, 9-diamantantriol, and the like.
- 1,4,6-diamantanetriol represented by the following formula (12) is obtained.
- R 4 has the same meaning as in formula (1) ⁇
- 1, 4, 6-diamantanetriols represented by formula (1 2) a preferred compound is specifically exemplified.
- 1,4,6-diamantantriol, 9-methyl-1,4,6-diamantantriol, 9-ethyl-1,4,6-diamantantriol and the like can be mentioned.
- the method for isolating the diamantane polyols produced by the above reaction is not particularly limited, and can be carried out, for example, by the following method. That is, after completion of the reaction, the reaction solution is cooled to room temperature, and the pressure in the autoclave is returned to normal pressure.
- the precipitated solid is separated by a technique such as filtration or centrifugation to obtain a solid.
- the obtained solid usually contains an alkali metal halide salt formed as a by-product of a reaction between a hydrogen halide produced by hydrolysis of polyhalogenated diamantanes and a carboxylate.
- the alkali metal halide salt can be removed by washing the solid with water.
- a crude product of diamantane polyols conversion rate of dihalogenated diamantane of the raw material is usually 95% or more
- the reaction solution is concentrated, and the concentrated reaction solution is extracted using an alcohol such as butanol, and then the extract is further concentrated to obtain a crude diamantane polyol. it can.
- the method for purifying the crude product of diamantane polyols isolated in this manner is not particularly limited, but the following method is preferred, for example.
- impurities dissolve, but diamantane polyols do not dissolve or are difficult to dissolve organic solvents (poor solvents), That is, an organic solvent (hereinafter also referred to as a reslurry solvent) that selectively dissolves impurities contained in a crude product of diamantane polyols is added to the crude product to form a slurry. The slurry is then filtered to remove the filtrate, and then the crude product is dried. By this operation, high purity diamantane polyols (usually diamantane polyol) It contains 95 mol% or more of mono. (Hereinafter, this process is also called reslurry process).
- halogenated aliphatic hydrocarbons such as methylene chloride, black mouth form, carbon tetrachloride, hexane, heptane, octane, etc.
- Aliphatic hydrocarbons such as black benzene, bromobenzene, dichlorobenzene, and dibutyl benzene
- ethers such as jetyl ether, dipropyl ether, and dibutyl ether
- methyl acetate Preferred are esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and cyan compounds such as acetonitrile.
- adsorption treatment such as activated carbon treatment, silica treatment, alumina treatment, etc. can remove various impurities, further improve the purity, and further decolorization (removal of color derived from impurities) The degree of will also increase.
- purification by a known method such as recrystallization or sublimation purification can provide a higher-purity target product.
- the purity of the target product can be confirmed by gas chromatography (G C).
- the resulting dichloroamantane was almost selectively 4,9-dichlorodiamantane.
- Example 1 the amount of chlorosulfonic acid used is shown in Table 1. The operation was the same except that the change was made to. The results are shown in Table 1. table 1
- Fig. 1 shows the nuclear magnetic resonance (NMR) spectrum of the proton
- Fig. 2 shows the nuclear magnetic resonance (NMR) spectrum of the force.
- the obtained trichlorodiamantane was 1, 4, 9-trichlorodiamantane almost selectively.
- Example 8 The reaction and post-treatment were carried out in the same manner as in Example 6. N-heptane was added to 150 g of the obtained crude product (5 times by weight of the obtained trichlorodiamantan crude product), and 90 g of chloroform (3 times by weight of the obtained trichlorodiamantan crude product). ) was added and heated to reflux for 1 hour. After heating at reflux for 1 hour, the crude trichlorodiamantane had dissolved and was a homogeneous solution. Thereafter, the mixture was cooled to 5 ° C. and further stirred and aged for 1 hour.
- Fig. 3 shows the nuclear magnetic resonance (NMR) spectrum of the proton
- Fig. 4 shows the nuclear magnetic resonance (NMR) spectrum of the force. From this spectrum, it can be seen that the trichlorodiamantane obtained by this production method is almost selectively 1,4,9-trichlorodiamantane.
- Example 8 the same operation as in Example 1 was carried out except that the amount of sodium chloride to be added was changed as shown in Table 2. The color of the obtained solid was observed. These results are shown in Table 2.
- the reaction solution was cooled to about 5, and 30 g of water was added dropwise while taking care that the reaction solution did not exceed 30 ° C. 140 g of methylene chloride was added and stirred. After standing, the lower sulfuric acid aqueous solution layer was separated. After that, the organic layer was washed three times, once with 40 g of 10% by weight aqueous sodium hydroxide solution, twice with 40 g and 20 g of 7% by weight aqueous sodium sulfate solution. The pH of the layer became neutral. The organic layer was concentrated under reduced pressure to obtain 28 g (containing 80% dichlorodiamantane) cream-colored solid. Yield 82% (based on diamantane) The obtained dichloroamantane was almost selectively 4,9-dichlorodiamantane.
- Example 1 3 Under a nitrogen stream, 40 g of concentrated sulfuric acid (2 mass times that of diamantan), 1.5 g of sodium sulfate (0.01 0 6 mol, 0.1% of diamantane) Mole times). Further, 20 g (0.16 6mo 1) of diamantane was added, and the mixture was stirred for 10 minutes while being kept at about 20 ° C. in a suspended state. To this, 61.8 g of chlorosulfonic acid (0.5 3 mol, 5 mol times of diamantane) was gradually added so that the reaction would not run away. When chlorosulfonic acid was charged, chlorosulfonic acid reacted fairly vigorously, so that the charging time was longer than that in Example 1.
- the dichloroamantane obtained was almost selectively 4,9-dichlorodiamantane.
- Example 3 The same operation as in Example 1 was carried out except that the diamantane used in Example 1 was changed as shown in Table 3. The results are shown in Table 3. Table 3
- Figure 5 shows the nuclear magnetic resonance (NMR) spectrum of protons.
- NMR nuclear magnetic resonance
- Fig. 6 shows the nuclear magnetic resonance (NMR) spectrum of proton
- Fig. 7 shows the nuclear magnetic resonance (NMR) spectrum of carbon.
- Example 17 The same operation as in Example 17 was carried out except that the reslurry solvent used was changed to that shown in Table 4. Table 4 shows the results. Table 4
- Example 17 The same operation as in Example 17 was carried out except that the carboxylate shown in Table 5 was used in place of sodium acetate in Example 17. Table 5 shows the results. Table 5
- Fig. 8 shows the nuclear magnetic resonance (NMR) spectrum of proton
- Fig. 9 shows the nuclear magnetic resonance (NMR) spectrum of carbon.
- Example 23 the same operation was carried out except that the monolithic solvent used was changed to that shown in Table 6. The results are shown in Table 6.
- Example 23 the same operation as in Example 23 was performed, except that the carboxylate shown in Table 7 was used instead of sodium acetate. The results are shown in Table 7. Table 7
Abstract
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KR1020067027135A KR100888124B1 (ko) | 2004-06-23 | 2005-06-20 | 폴리할로겐화 디아만탄류 및 그의 유도체의 제조 방법 |
EP05752842A EP1760057A4 (en) | 2004-06-23 | 2005-06-20 | METHOD FOR PRODUCING POLYHALOGENATED DIAMANTAN AND DERIVATIVES THEREOF |
JP2006528647A JP4611984B2 (ja) | 2004-06-23 | 2005-06-20 | ポリハロゲン化ジアマンタン類及びその誘導体の製造方法 |
CN2005800207805A CN1972886B (zh) | 2004-06-23 | 2005-06-20 | 多卤代金刚十四烷类及其衍生物的制造方法 |
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JP2008106053A (ja) * | 2006-09-25 | 2008-05-08 | Fujifilm Corp | 4,9−ジブロモジアマンタンの製造方法 |
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US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
US20050038310A1 (en) | 2003-07-15 | 2005-02-17 | Lorkovic Ivan M. | Hydrocarbon synthesis |
US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
US20080009546A1 (en) * | 2005-05-06 | 2008-01-10 | Chevron U.S.A. Inc. | Diamondoid derivatives possessing therapeutic activity in the treatment of neurologic disorders |
AP2012006510A0 (en) | 2006-02-03 | 2012-10-31 | Grt Inc | Continuous process for converting natural gas to liquid hydrocarbons |
EP1993951B1 (en) | 2006-02-03 | 2014-07-30 | GRT, Inc. | Separation of light gases from bromine |
MX2009012581A (es) | 2007-05-24 | 2010-03-15 | Grt Inc | Reactor de zonas que incorpora captura y liberacion de haluro de hidrogeno reversible. |
US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
US8415517B2 (en) | 2008-07-18 | 2013-04-09 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
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EP1760057A4 (en) | 2008-05-21 |
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