TW201402529A - Method for producing adamantanetriol - Google Patents

Method for producing adamantanetriol Download PDF

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TW201402529A
TW201402529A TW102120191A TW102120191A TW201402529A TW 201402529 A TW201402529 A TW 201402529A TW 102120191 A TW102120191 A TW 102120191A TW 102120191 A TW102120191 A TW 102120191A TW 201402529 A TW201402529 A TW 201402529A
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adamantane
producing
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adamantane triol
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Junichi UCHITA
Yoshikazu Aoki
Tsuyoshi Sato
Taito Muraoka
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Hodogaya Chemical Co Ltd
Nippon Peroxide Co Ltd
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    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
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    • C07C2603/74—Adamantanes

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Abstract

The present invention relates to a method for producing an adamantanetriol whereby an adamantane represented by general formula (1) is reacted with hydrogen peroxide in a solvent and in the presence of a metal complex (in the formula, R is a halogen atom, hydroxyl group, C1-10 alkyl group, C3-10 cycloalkyl group, C1-10 alkoxy group, C3-10 cycloalkoxy group, C2-10 acyl group, C2-10 acyloxy group, aryl group, or aryloxy group; n is an integer between 0 and 13; and the number of hydroxyl groups is 2 or less).

Description

金剛烷三醇類之製造方法 Method for producing adamantane triol

本發明係關於一種以高選擇性且高產率自金剛烷類製造金剛烷三醇類之方法。 The present invention relates to a process for producing adamantane triols from adamantanes with high selectivity and high yield.

於金剛烷骨架上經羥基取代之金剛烷醇類係作為高功能性聚合物或電子材料、合成潤滑油、或醫農藥等之中間物而有用之化合物。 Adamantyl alcohol substituted with a hydroxy group on the adamantane skeleton is a compound useful as an intermediate between a highly functional polymer, an electronic material, a synthetic lubricating oil, or a medical pesticide.

作為金剛烷醇類之製造方法，已知有於三級胺化合物之存在下使溴金剛烷水解之方法(例如參照專利文獻1)、於觸媒量之釕化合物存在下使金剛烷與次氯酸鹽於水/有機溶劑的2相系中反應之方法(例如參照專利文獻2)、以N-羥基鄰苯二甲醯亞胺作為觸媒而使金剛烷氧氧化之方法(例如參照專利文獻3)、藉由三氧化鉻而使金剛烷氧化之方法(例如參照專利文獻4)等。 As a method for producing an adamantyl alcohol, a method of hydrolyzing bromoadamantane in the presence of a tertiary amine compound (for example, refer to Patent Document 1) and adamantane and hypochlorous in the presence of a catalyst amount of a ruthenium compound are known. A method of reacting an acid salt in a two-phase system of water/organic solvent (for example, refer to Patent Document 2), and a method of oxidizing adamantane by using N-hydroxyphthalimide as a catalyst (for example, refer to the patent literature) 3) A method of oxidizing adamantane by using chromium trioxide (for example, refer to Patent Document 4).

然而，於專利文獻1中，需要150℃~280℃之高溫條件，需要合成起始原料之溴化物之前期步驟，而且混入有來自原料之溴化物，其純化較為困難。於專利文獻2中，必需將反應系統內之pH值控制在固定範圍內，所得之產物為金剛烷二醇。又，於專利文獻3中，產物之選擇性較低，所得之金剛烷醇類之分離需要繁雜之操作。進而，於專利文獻4中，必需大量使用毒性較高之六價鉻，有環境負荷方面之問題。 However, in Patent Document 1, high temperature conditions of 150 ° C to 280 ° C are required, and a preliminary step of synthesizing the bromide of the starting material is required, and bromide derived from the raw material is mixed, which is difficult to purify. In Patent Document 2, it is necessary to control the pH in the reaction system within a fixed range, and the obtained product is adamantanediol. Further, in Patent Document 3, the selectivity of the product is low, and the separation of the obtained adamantyl alcohol requires complicated operations. Further, in Patent Document 4, it is necessary to use a large amount of hexavalent chromium which is highly toxic, and there is a problem in environmental load.

另一方面，亦已知有藉由使用環境負荷更低之過氧化氫之氧化反應而將金剛烷類製成金剛烷醇類的方法，例如於非專利文獻1中， 使用錸觸媒與過氧化氫於60℃下進行金剛烷之氧化反應。然而，所得之產物僅為金剛烷單醇與少量之金剛烷二醇。 On the other hand, there is also known a method of forming an adamantane into an adamantyl alcohol by using an oxidation reaction of hydrogen peroxide having a lower environmental load, for example, in Non-Patent Document 1, The oxidation reaction of adamantane was carried out using a ruthenium catalyst and hydrogen peroxide at 60 °C. However, the resulting product is only adamantane monol and a small amount of adamantane diol.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平2-196744號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 2-196744

[專利文獻2]日本專利特開2002-167342號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-167342

[專利文獻3]日本專利特開平10-286467號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 10-286467

[專利文獻4]日本專利特開2003-321408號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-321408

[非專利文獻] [Non-patent literature]

[非專利文獻1]Tetrahedron Letters,36,6415(1995) [Non-Patent Document 1] Tetrahedron Letters, 36, 6415 (1995)

[非專利文獻2]Science,318,783(2007) [Non-Patent Document 2] Science, 318, 783 (2007)

[非專利文獻3]Inorganic Chemistry,44,8125(2005) [Non-Patent Document 3] Inorganic Chemistry, 44, 8125 (2005)

如此，雖然已知有多種製造金剛烷醇類之方法，但使用過氧化氫作為氧化劑之例較少，尤其是控制導入至金剛烷環上之羥基之數量並以高選擇性且高產率獲得金剛烷三醇類的方法尚不為人知。本發明之目的在於提供一種金剛烷三醇類之製造方法，其藉由進行使用過氧化氫之氧化反應，可降低能量成本及環境負荷，進而可以高選擇性且高產率獲得金剛烷三醇類。 Thus, although various methods for producing adamantyl alcohols are known, there are few examples of using hydrogen peroxide as an oxidizing agent, in particular, controlling the amount of hydroxyl groups introduced into the adamantane ring and obtaining the diamond in high selectivity and high yield. The methods of alkanols are not known. An object of the present invention is to provide a method for producing adamantane triol, which can reduce energy cost and environmental load by performing oxidation reaction using hydrogen peroxide, thereby obtaining adamantane triol with high selectivity and high yield. .

本發明者等人為了達成上述目的而反覆潛心研究，結果發現，藉由於溶劑中且於金屬錯合物之存在下利用過氧化氫使金剛烷類氧化，可以高選擇性且高產率獲得金剛烷三醇類。即，本發明係將以下作為主旨。 The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, have found that adamantane can be obtained with high selectivity and high yield by oxidizing adamantane by using hydrogen peroxide in a solvent and in the presence of a metal complex. Triols. That is, the present invention is as follows.

1.一種金剛烷三醇類之製造方法，其係使下述通式(1)所表示之金 剛烷類於溶劑中且於金屬錯合物之存在下與過氧化氫反應。 A method for producing an adamantane triol, which is a gold represented by the following formula (1) The cycloalkanes are reacted with hydrogen peroxide in a solvent and in the presence of a metal complex.

式中，R表示鹵素原子、羥基、可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷基、可具有取代基之碳原子數3~10之環烷基、可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷氧基、可具有取代基之碳原子數3~10之環烷氧基、可具有取代基之碳原子數2~10之醯基、可具有取代基之碳原子數2~10之醯氧基、經取代或未經取代之芳基、經取代或未經取代之芳氧基。n表示0~13之整數。於n為2以上之情形時，複數個R相互可相同亦可不同。其中，羥基之數量為兩個以下。 In the formula, R represents a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, and a linear or branched alkoxy group having 1 to 10 carbon atoms having a substituent, a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, and 2 to 10 carbon atoms which may have a substituent A mercapto group of 10, an alkylene group having 2 to 10 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group. n represents an integer from 0 to 13. When n is 2 or more, the plurality of Rs may be the same or different from each other. Among them, the number of hydroxyl groups is two or less.

2.如上述1之金剛烷三醇類之製造方法，其中使上述通式(1)所表示之金剛烷類於溶劑中且於金屬錯合物及有機酸之存在下與過氧化氫反應。 2. The method for producing an adamantane triol according to the above 1, wherein the adamantane represented by the above formula (1) is reacted with hydrogen peroxide in a solvent in the presence of a metal complex and an organic acid.

3.如上述1或2之金剛烷三醇類之製造方法，其中上述金剛烷三醇類為1,3,5-金剛烷三醇衍生物。 3. The method for producing adamantane triol according to 1 or 2 above, wherein the adamantane triol is a 1,3,5-adamantane triol derivative.

4.如上述1至3中任一項之金剛烷三醇類之製造方法，其中上述溶劑為水/有機溶劑之混合溶液。 4. The method for producing an adamantane triol according to any one of the above 1 to 3, wherein the solvent is a mixed solution of water/organic solvent.

5.如上述4之金剛烷三醇類之製造方法，其中上述有機溶劑為選自水溶性之醇類或腈類中之一種或兩種以上之有機溶劑。 5. The method for producing adamantane triol according to the above 4, wherein the organic solvent is one or more organic solvents selected from the group consisting of water-soluble alcohols and nitriles.

6.如上述4之金剛烷三醇類之製造方法，其中上述有機溶劑為乙腈。 6. The method for producing adamantane triol according to the above 4, wherein the organic solvent is acetonitrile.

7.如上述1至6中任一項之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，配位子之至少一個具有4~8個氮原子，其中複數個氮原子經由連續之2個碳原子而連結。 7. The method for producing an adamantane triol according to any one of the above 1 to 6, wherein in the metal complex, at least one of the ligands has 4 to 8 nitrogen atoms, wherein the plurality of nitrogen atoms are via Two consecutive carbon atoms are connected.

8.如上述7之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，配位子之至少一個為下述通式(2)或(3)所表示之含氮化合物。 8. The method for producing adamantane triol according to the above 7, wherein at least one of the ligands is a nitrogen-containing compound represented by the following formula (2) or (3).

式中，R1~R4可相同亦可不同，表示氫原子或可具有取代基之碳原子數1~10之直鏈狀或支鏈狀之烷基。Ar1及Ar2可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基。 In the formula, R 1 to R 4 may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent. Ar 1 and Ar 2 may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

式中，Ar3~Ar5可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基。 In the formula, Ar 3 to Ar 5 may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

9.如上述8之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，通式(2)中之R1~R4之鄰接之對中的至少一對以經由單鍵形成環之方式連結。 9. The method for producing adamantane triol according to the above 8, wherein in the metal complex, at least one pair of adjacent pairs of R 1 to R 4 in the formula (2) is formed via a single bond. Linked by way.

10.如上述9之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，通式(2)中之R1~R4之鄰接之對中的R1與R2及R3與R4分別以經由單鍵形成環之方式連結。 10. The method for producing adamantane triol according to the above 9, wherein in the metal complex, R 1 and R 2 and R 3 in the adjacent pair of R 1 to R 4 in the formula (2) Each of R 4 is linked to form a ring via a single bond.

11.如上述1~10中任一項之金剛烷三醇類之製造方法，其中上述金屬錯合物之中心金屬為選自過渡金屬中之金屬。 The method for producing an adamantane triol according to any one of the above 1 to 10, wherein the central metal of the metal complex is a metal selected from the group consisting of transition metals.

12.如上述11之金剛烷三醇類之製造方法，其中上述金屬錯合物之中心金屬為鐵。 12. The method for producing adamantane triol according to the above 11, wherein the central metal of the metal complex is iron.

13.如上述2之金剛烷三醇類之製造方法，其中上述有機酸為脂肪族羧酸或芳香族羧酸。 13. The method for producing adamantane triol according to the above 2, wherein the organic acid is an aliphatic carboxylic acid or an aromatic carboxylic acid.

14.如上述13之金剛烷三醇類之製造方法，其中上述有機酸為乙酸。 14. The method for producing adamantane triol according to the above 13, wherein the organic acid is acetic acid.

根據本發明，可藉由以金剛烷類作為起始原料、廉價且環境負荷較少之方法而以高選擇性且高產率製造金剛烷三醇類。 According to the present invention, adamantane triols can be produced with high selectivity and high yield by a method in which adamantane is used as a starting material, inexpensive and environmentally less loaded.

以下，對本發明之實施形態進行詳細說明。於本發明中用作起始原料之金剛烷類係下述通式(1)所表示者。 Hereinafter, embodiments of the present invention will be described in detail. The adamantane used as a starting material in the present invention is represented by the following formula (1).

式中，R表示鹵素原子、羥基、可具有取代基之直鏈狀或支鏈狀 之碳原子數1~10之烷基、可具有取代基之碳原子數3~10之環烷基、可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷氧基、可具有取代基之碳原子數3~10之環烷氧基、可具有取代基之碳原子數2~10之醯基、可具有取代基之碳原子數2~10之醯氧基、經取代或未經取代之芳基、經取代或未經取代之芳氧基。n表示0~13之整數。於n為2以上之情形時，複數個R相互可相同亦可不同。其中，羥基之數量為兩個以下。 Wherein R represents a halogen atom, a hydroxyl group, a linear or branched chain which may have a substituent An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, a mercapto group having 2 to 10 carbon atoms which may have a substituent, an anthracene group having 2 to 10 carbon atoms which may have a substituent, Substituted or unsubstituted aryl, substituted or unsubstituted aryloxy. n represents an integer from 0 to 13. When n is 2 or more, the plurality of Rs may be the same or different from each other. Among them, the number of hydroxyl groups is two or less.

作為通式(1)中之R所表示之「鹵素原子」、「可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷基」、「可具有取代基之碳原子數3~10之環烷基」、「可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷氧基」、「可具有取代基之碳原子數3~10之環烷氧基」、「可具有取代基之碳原子數2~10之直鏈狀或支鏈狀之醯基」及「可具有取代基之碳原子數2~10之醯氧基」中的「鹵素原子」、「碳原子數1~10之烷基」、「碳原子數3~10之環烷基」、「碳原子數1~10之烷氧基」、「碳原子數3~10之環烷氧基」、「碳原子數2~10之醯基」及「碳原子數2~10之醯氧基」，具體而言，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基；環丙基、環戊基、環己基、環辛基等環烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀烷氧基；異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀烷氧基；環丙氧基、環戊氧基、環己氧基、環丙基甲氧基等環烷氧基；乙醯基、丙醯基、丁醯基、異丁醯基、戊醯基、己醯基、庚醯基、辛醯基、苯甲醯基、庚醯基、環己羰基等直鏈狀或支鏈狀之醯基；及乙醯氧基、丙醯氧基、丁醯氧基、戊醯氧基、己醯氧基等醯氧基。 "Halogen atom" represented by R in the general formula (1), "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent", and "carbon atom which may have a substituent" a cycloalkyl group of 3 to 10", a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a ring of 3 to 10 carbon atoms which may have a substituent. "alkoxy", "linear or branched fluorenyl group having 2 to 10 carbon atoms which may have a substituent" and "oxyl group having 2 to 10 carbon atoms which may have a substituent" Halogen atom", "alkyl group having 1 to 10 carbon atoms", "cycloalkyl group having 3 to 10 carbon atoms", "alkoxy group having 1 to 10 carbon atoms", and "3 to 10 carbon atoms" The cycloalkoxy group, the "fluorenyl group having 2 to 10 carbon atoms" and the "oxyl group having 2 to 10 carbon atoms" include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. a halogen atom; a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group; an isopropyl group, an isobutyl group, a second butyl group; a branched alkyl group such as a tributyl group or an isooctyl group; a cycloalkyl group such as a propyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a linear alkoxy group such as a decyloxy group or a decyloxy group; a branched alkoxy group such as an isopropoxy group, an isobutoxy group, a second butoxy group, a third butoxy group or an isooctyloxy group; a cycloalkyloxy group such as a propoxy group, a cyclopentyloxy group, a cyclohexyloxy group or a cyclopropylmethoxy group; an ethyl group, a propyl group, a butyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a fluorenyl group a linear or branched fluorenyl group such as octyl decyl, benzylidene, heptyl carbonyl or cyclohexylcarbonyl; and ethoxylated, propyloxy, butyloxy, pentyloxy, hexanyl An oxy group such as an oxy group.

作為通式(1)中之R所表示之「可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷基」、「可具有取代基之碳原子數3~10之環烷基」、「可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷氧基」、「可具有取代基之碳原子數3~10之環烷氧基」、「可具有取代基之碳原子數2~10之直鏈狀或支鏈狀之醯基」及「可具有取代基之碳原子數2~10之醯氧基」中的「取代基」，具體而言，可列舉：鹵素原子、碳原子數1至10之直鏈狀或支鏈狀之烷基、碳原子數3至10之環烷基、碳原子數1至10之直鏈狀或支鏈狀之烷氧基、碳原子數3至10之環烷氧基、碳原子數1至10之鹵代烷基、碳原子數1至10之直鏈狀或支鏈狀之鹵代烷氧基等。具體而言，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基；環丙基、環戊基、環己基、環辛基等環烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀烷氧基；異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀烷氧基；環丙氧基、環戊氧基、環己氧基、環丙基甲氧基等環烷氧基；三氟甲基、五氟乙基、九氟丁基、三氟甲氧基等鹵代烷基或鹵代烷氧基等。 The linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R in the formula (1), and the carbon atom which may have a substituent of 3 to 10 a cycloalkyl group, a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a cycloalkyloxy group having 3 to 10 carbon atoms which may have a substituent, "Substituent" in the "linear or branched fluorenyl group having 2 to 10 carbon atoms which may have a substituent" and "oxyl group having 2 to 10 carbon atoms which may have a substituent", specifically In addition, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched carbon number of 1 to 10 may be mentioned. a chain alkoxy group, a cycloalkyloxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a linear or branched haloalkoxy group having 1 to 10 carbon atoms, and the like. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. A straight-chain alkyl group; a branched alkyl group such as isopropyl, isobutyl, t-butyl, t-butyl or isooctyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. Cycloalkyl; linear alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy a branched alkoxy group such as isopropoxy group, isobutoxy group, second butoxy group, third butoxy group or isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, a cycloalkyloxy group such as a cyclopropylmethoxy group; a halogenated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group or a trifluoromethoxy group; or a halogenated alkoxy group.

作為通式(1)中之R所表示之「經取代或未經取代之芳基」及「經取代或未經取代之芳氧基」中的「芳基」及「芳氧基」，具體而言，可列舉：苯基、萘基、聯苯基、薁基、蒽基、聯三苯基、芘基、菲基等碳原子數6至20之芳香族烴基或縮合多環芳香族基；苯氧基等芳氧基。 As the "aryl" and "aryloxy" in the "substituted or unsubstituted aryl group" represented by R in the formula (1) and the "substituted or unsubstituted aryloxy group", Examples thereof include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a fluorenyl group, a terphenyl group, a fluorenyl group, and a phenanthryl group, or a condensed polycyclic aromatic group. An aryloxy group such as a phenoxy group.

作為通式(1)中之R所表示之「經取代之芳基」及「經取代之芳氧基」中的「取代基」，具體而言，可列舉：鹵素原子、碳原子數1至10之直鏈狀或支鏈狀之烷基、碳原子數3至10之環烷基、碳原子數1至10 之直鏈狀或支鏈狀之烷氧基、碳原子數3至10之環烷氧基、碳原子數1至10之鹵代烷基、碳原子數1至10之直鏈狀或支鏈狀之鹵代烷氧基等。具體而言，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基；環丙基、環戊基、環己基、環辛基等環烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀烷氧基；異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀烷氧基；環丙氧基、環戊氧基、環己氧基、環丙基甲氧基等環烷氧基；三氟甲基、五氟乙基、九氟丁基、三氟甲氧基等鹵代烷基或鹵代烷氧基等。 Specific examples of the "substituent" in the "substituted aryl group" and the "substituted aryloxy group" represented by R in the formula (1) include a halogen atom and a carbon number of 1 to a linear or branched alkyl group of 10, a cycloalkyl group having 3 to 10 carbon atoms, and 1 to 10 carbon atoms a linear or branched alkoxy group, a cycloalkyloxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms. Haloalkoxy and the like. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. A straight-chain alkyl group; a branched alkyl group such as isopropyl, isobutyl, t-butyl, t-butyl or isooctyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. Cycloalkyl; linear alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy a branched alkoxy group such as isopropoxy group, isobutoxy group, second butoxy group, third butoxy group or isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, a cycloalkyloxy group such as a cyclopropylmethoxy group; a halogenated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group or a trifluoromethoxy group; or a halogenated alkoxy group.

通式(1)中之n表示0~13之整數，就反應性及獲得之容易性等而言，尤佳為0~3之整數。 n in the general formula (1) represents an integer of 0 to 13, and is particularly preferably an integer of 0 to 3 in terms of reactivity and ease of availability.

作為通式(1)所表示之金剛烷類，具體而言，可列舉：金剛烷、1-金剛烷醇、2-金剛烷醇、1,3-金剛烷二醇、1-氟金剛烷、2-氟金剛烷、1,3-二氟金剛烷、1,3,5-三氟金剛烷、1-氯金剛烷、2-氯金剛烷、1,3-二氯金剛烷、1,3,5-三氯金剛烷、1-溴金剛烷、2-溴金剛烷、1,3-二溴金剛烷、1,3,5-三溴金剛烷、1-甲基金剛烷、2-甲基金剛烷、1,3-二甲基金剛烷、1,3,5-三甲基金剛烷、1-乙基金剛烷、2-乙基金剛烷、1,3-二乙基金剛烷、1,3,5-三乙基金剛烷、1-丙基金剛烷、2-丙基金剛烷、1,3-二丙基金剛烷、1,3,5-三丙基金剛烷、1-苯基金剛烷、2-苯基金剛烷、1,3-二苯基金剛烷、1,3,5-三苯基金剛烷、1-乙醯氧基金剛烷、2-乙醯氧基金剛烷、1,3-二乙醯氧基金剛烷、1,3,5-三乙醯氧基金剛烷、1-甲氧基金剛烷、2-甲氧基金剛烷、1,3-二甲氧基金剛烷、1,3,5-三甲氧基金剛烷等，就反應性及獲得之容易性等而言，尤佳為金剛烷、1-金剛烷醇、2-金剛烷醇、1,3-金剛烷二醇。 Specific examples of the adamantane represented by the formula (1) include adamantane, 1-adamantanol, 2-adamantanol, 1,3-adamantanediol, and 1-fluoroadamantane. 2-fluoroadamantane, 1,3-difluoroadamantane, 1,3,5-trifluoroadamantane, 1-chloroadamantane, 2-chloroadamantane, 1,3-dichloroadamantane, 1,3 , 5-trichloroadamantane, 1-bromodamantane, 2-bromoamantane, 1,3-dibromoamantane, 1,3,5-tribromonadamantane, 1-methyladamantane, 2-methyl Fundane, 1,3-dimethyl adamantane, 1,3,5-trimethyladamantane, 1-ethyladamantane, 2-ethyladamantane, 1,3-diethyladamantane, 1,3,5-triethyladamantane, 1-propyladamantane, 2-propyladamantane, 1,3-dipropyladamantane, 1,3,5-tripropyladamantane, 1- Phenyl adamantane, 2-phenyladamantane, 1,3-diphenyladamantane, 1,3,5-triphenyladamantane, 1-ethenyloxyadamantane, 2-ethenyloxygold Alkane, 1,3-diethoxydecane adamantane, 1,3,5-triethoxydecane adamantane, 1-methoxyadamantane, 2-methoxyadamantane, 1,3-dimethyl Oxyadamantane, 1,3,5-trimethoxyadamantane, etc., are easy to react and obtain For the like, and particularly preferably adamantane, 1-adamantanol, 2-adamantanol, 1,3-adamantanediol.

藉由本發明所得之金剛烷三醇類為於金剛烷骨架上取代有3個羥基之化合物。3個羥基之取代位置並無特別限定，於使用取代有羥基之金剛烷類作為起始原料之情形時，所得之產物係不論取代位置而於金剛烷骨架上取代3個羥基者。於金剛烷骨架上之4個三級碳(橋頭碳)未經取代之情形時，該位置會優先被氧化，因此於本發明中，可以最高選擇性且最高產率獲得1,3,5-金剛烷三醇衍生物。 The adamantane triol obtained by the present invention is a compound in which three hydroxyl groups are substituted on the adamantane skeleton. The position of substitution of the three hydroxyl groups is not particularly limited. When adamantane substituted with a hydroxyl group is used as a starting material, the obtained product is one in which three hydroxyl groups are substituted on the adamantane skeleton regardless of the position of substitution. When four tertiary carbons (bridgehead carbons) on the adamantane skeleton are unsubstituted, the position is preferentially oxidized, so that in the present invention, 1,3,5- can be obtained with the highest selectivity and highest yield. Adamantane triol derivative.

本發明所使用之金屬錯合物可單獨使用，亦可混合兩種以上而使用。作為金屬錯合物，並無特別限制，較佳為以鈦、釩、錳、鐵、鈷、鎳、銅、鉬、釕、鈀、鎢、錸、銥等過渡金屬作為中心金屬之金屬錯合物。該等之中，更佳為以鈦、釩、錳、鐵、鈷、鎳、銅等第一過渡金屬作為中心金屬之金屬錯合物，尤佳為鐵錯合物。 The metal complex used in the present invention may be used singly or in combination of two or more. The metal complex is not particularly limited, and is preferably a metal misalignment using a transition metal such as titanium, vanadium, manganese, iron, cobalt, nickel, copper, molybdenum, niobium, palladium, tungsten, rhenium or iridium as a central metal. Things. Among these, a metal complex which is a central metal such as titanium, vanadium, manganese, iron, cobalt, nickel or copper is more preferable, and an iron complex is particularly preferable.

形成本發明所使用之金屬錯合物之配位子可為中性分子，亦可為陰離子，配位子之數量可為一個，亦可為兩個，於為兩個以上之情形時，分別可相同亦可不同。作為配位子，具體而言，可列舉：氯化物離子、溴化物離子等鹵化物離子；氫氧化物離子；氰化物離子；乙酸離子、丙酸離子等羧酸離子；硝酸離子；亞硝酸離子；碳酸離子；2,4-戊二酮、2,4-己二酮等β-二酮陰離子；氧分子；一氧化碳；水；羥基化合物；甲氧基化合物、乙氧基化合物、丙氧基化合物、丁氧基化合物等烷氧基化合物；乙烯、丙烯、苯乙烯、環戊二烯、環辛二烯等烯烴；二甲醚、二***等醚；乙腈、苯甲腈等腈化合物；三-第三丁基膦、三苯基膦等含磷化合物；氨、三甲胺、三乙胺、乙二胺、吡啶、啡啉、其他胺化合物等。 The ligand forming the metal complex used in the present invention may be a neutral molecule or an anion, and the number of the ligands may be one or two, and in the case of two or more, respectively Can be the same or different. Specific examples of the ligand include a halide ion such as a chloride ion or a bromide ion; a hydroxide ion; a cyanide ion; a carboxylate ion such as an acetate ion or a propionic acid ion; a nitrate ion; and a nitrite ion. Carbonate ion; β-diketone anion such as 2,4-pentanedione or 2,4-hexanedione; oxygen molecule; carbon monoxide; water; hydroxy compound; methoxy compound, ethoxy compound, propoxy compound An alkoxy compound such as a butoxy compound; an olefin such as ethylene, propylene, styrene, cyclopentadiene or cyclooctadiene; an ether such as dimethyl ether or diethyl ether; a nitrile compound such as acetonitrile or benzonitrile; A phosphorus-containing compound such as a third butylphosphine or a triphenylphosphine; ammonia, trimethylamine, triethylamine, ethylenediamine, pyridine, morpholine, or other amine compound.

可較佳地用於本發明之金屬錯合物含有至少一種上述胺化合物作為配位子。作為上述胺化合物，較佳為具有含有4~8個氮原子且其中複數個氮原子經由連續之2個碳原子連結的結構之化合物。上述具有含有4~8個氮原子且其中複數個氮原子經由連續之2個碳原子連結 的結構之化合物中之氮原子之個數更佳為4~6個，尤佳為4個或5個。經由連續之2個碳原子連結之氮原子之個數較佳為3個以上，更佳為4個或5個，尤佳為4個。作為上述具有含有4~8個氮原子且其中複數個氮原子經由連續之2個碳原子連結的結構之化合物，具體而言，可列舉下述通式(2)或(3)所表示之化合物。 The metal complex which can be preferably used in the present invention contains at least one of the above amine compounds as a ligand. The amine compound is preferably a compound having a structure of 4 to 8 nitrogen atoms in which a plurality of nitrogen atoms are bonded via two consecutive carbon atoms. The above has 4 to 8 nitrogen atoms and wherein a plurality of nitrogen atoms are linked via two consecutive carbon atoms The number of nitrogen atoms in the compound of the structure is preferably 4 to 6, more preferably 4 or 5. The number of nitrogen atoms to be bonded via two consecutive carbon atoms is preferably three or more, more preferably four or five, and particularly preferably four. The compound having a structure having 4 to 8 nitrogen atoms and having a plurality of nitrogen atoms bonded via two consecutive carbon atoms, specifically, a compound represented by the following formula (2) or (3) .

式中，R1~R4可相同亦可不同，表示氫原子或可具有取代基之碳原子數1~10之直鏈狀或支鏈狀之烷基。R1與R2、R2與R3、R3與R4可相互鍵結而形成環。Ar1及Ar2可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基。 In the formula, R 1 to R 4 may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent. R 1 and R 2 , R 2 and R 3 , and R 3 and R 4 may be bonded to each other to form a ring. Ar 1 and Ar 2 may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

式中，Ar3~Ar5可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基。 In the formula, Ar 3 to Ar 5 may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group.

作為通式(2)中之R1~R4所表示之「可具有取代基之碳原子數1~ 10之直鏈狀或支鏈狀之烷基」中的「碳原子數1~10之直鏈狀或支鏈狀之烷基」，具體而言，可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基。 "A carbon number of 1 to 10" in the "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" represented by R 1 to R 4 in the formula (2) The linear or branched alkyl group, specifically, a linear chain such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. An alkyl group; a branched alkyl group such as isopropyl, isobutyl, t-butyl, t-butyl or isooctyl.

通式(2)中之R1~R4鄰接之對R1與R2、R2與R3、R3與R4可相互連結而形成環，於該情形時，較佳為經由單鍵而連結者。作為所形成之環，較佳為環戊基環、環己基環、環辛基環等環烷基環；或吡咯啶環、哌啶環等雜環。即，較佳為於通式(2)中之R1~R4之鄰接之對中的至少一對以經由單鍵形成環之方式連結，尤佳為R1與R2、及R3與R4分別以經由單鍵形成環之方式連結。 When the formula R (2) 1 ~ R 4 in the adjacent pair of R 1 and R 2, R 2 and R 3, R 3 and R 4 may be bonded to each other to form a ring, in this case, preferably via a single bond And the linker. The ring to be formed is preferably a cycloalkyl ring such as a cyclopentyl ring, a cyclohexyl ring or a cyclooctyl ring; or a heterocyclic ring such as a pyrrolidine ring or a piperidine ring. That is, it is preferred that at least one pair of the adjacent pairs of R 1 to R 4 in the formula (2) is bonded via a single bond to form a ring, and more preferably R 1 and R 2 and R 3 are R 4 is bonded so as to form a ring via a single bond.

作為通式(2)中之R1~R4所表示之「可具有取代基之碳原子數1~10之直鏈狀或支鏈狀之烷基」中的「取代基」，具體而言，可列舉：鹵素原子、碳原子數1~10之直鏈狀或支鏈狀之烷基、碳原子數3~10之環烷基、碳原子數1~10之直鏈狀或支鏈狀之烷氧基、碳原子數3~10之環烷氧基、碳原子數1~10之直鏈狀或支鏈狀之鹵代烷基、碳原子數1~10之直鏈狀或支鏈狀之鹵代烷氧基、烷氧基羰基、硝基等。具體而言，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基；環丙基、環戊基、環己基、環辛基等環烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀烷氧基；異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀烷氧基；環丙氧基、環戊氧基、環己氧基、環丙基甲氧基等環烷氧基；三氟甲基、五氟乙基、九氟丁基、三氟甲氧基等鹵代烷基或鹵代烷氧基；甲氧基羰基、乙氧基羰基、丙氧基羰基等烷氧基羰基、硝基等。該等之中，較佳為鹵素原子、碳原子數1 ~10之直鏈狀或支鏈狀之烷基、碳原子數3~10之環烷基、碳原子數1~10之直鏈狀或支鏈狀之烷氧基、碳原子數3~10之環烷氧基，尤佳為鹵素原子、碳原子數1~5之直鏈狀或支鏈狀之烷基、碳原子數1~5之直鏈狀或支鏈狀之烷氧基。 The "substituent" in the "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" represented by R 1 to R 4 in the formula (2), specifically Examples thereof include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a linear or branched chain having 1 to 10 carbon atoms. Alkoxy group, cycloalkyloxy group having 3 to 10 carbon atoms, linear or branched haloalkyl group having 1 to 10 carbon atoms, linear or branched chain having 1 to 10 carbon atoms Haloalkoxy, alkoxycarbonyl, nitro, and the like. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. A straight-chain alkyl group; a branched alkyl group such as isopropyl, isobutyl, t-butyl, t-butyl or isooctyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. Cycloalkyl; linear alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy a branched alkoxy group such as isopropoxy group, isobutoxy group, second butoxy group, third butoxy group or isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, a cycloalkyloxy group such as a cyclopropylmethoxy group; a halogenated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group or a trifluoromethoxy group; or a halogenated alkoxy group; a methoxycarbonyl group, an ethoxycarbonyl group, An alkoxycarbonyl group such as a propoxycarbonyl group, a nitro group or the like. Among these, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a linear chain having 1 to 10 carbon atoms are preferable. Or a branched alkoxy group, a cycloalkyloxy group having 3 to 10 carbon atoms, particularly preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a carbon atom number of 1~ a linear or branched alkoxy group of 5.

作為R1~R4，尤佳為氫原子、可具有取代基之碳原子數1~5之直鏈狀或支鏈狀之烷基。 R 1 to R 4 are particularly preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms which may have a substituent.

作為通式(2)及(3)中之Ar1~Ar5所表示之「經取代或未經取代之含氮芳香族雜環基」中的「含氮芳香族雜環」，具體而言，可列舉：吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、吡環、唑環、噻唑環、喹啉環、異喹啉環、喹啉環、啉環、吲哚環、異吲哚環、苯并咪唑環等。 The "nitrogen-containing aromatic heterocyclic ring" in the "substituted or unsubstituted nitrogen-containing aromatic heterocyclic group" represented by Ar 1 to Ar 5 in the general formulae (2) and (3), specifically , for example, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridyl ring, Oxazole ring, thiazole ring, quinoline ring, isoquinoline ring, quin Porphyrin ring, A porphyrin ring, an anthracene ring, an isoindole ring, a benzimidazole ring or the like.

通式(2)及(3)所表示之化合物中所含之氮原子較佳為分別經由連續之2個碳原子而鍵結，Ar1~Ar5所表示之含氮芳香族雜環基之鍵結位置較佳為與該含氮芳香族雜環內之氮原子鄰接的碳原子。 The nitrogen atom contained in the compound represented by the general formulae (2) and (3) is preferably bonded via two consecutive carbon atoms, and the nitrogen-containing aromatic heterocyclic group represented by Ar 1 to Ar 5 is bonded. The bonding position is preferably a carbon atom adjacent to a nitrogen atom in the nitrogen-containing aromatic heterocyclic ring.

作為通式(2)及(3)中之Ar1~Ar5所表示之「經取代或未經取代之含氮芳香族雜環基」中的「取代基」，可列舉：鹵素原子、碳原子數1~10之直鏈狀或支鏈狀之烷基、碳原子數3~10之環烷基、碳原子數1~10之直鏈狀或支鏈狀之烷氧基、碳原子數3~10之環烷氧基、碳原子數1~10之直鏈狀或支鏈狀之鹵代烷基、碳原子數1~10之直鏈狀或支鏈狀之鹵代烷氧基、烷氧基羰基等。具體而言，可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子；甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等直鏈狀烷基；異丙基、異丁基、第二丁基、第三丁基、異辛基等支鏈狀烷基；環丙基、環戊基、環己基、環辛基等環烷基；甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基等直鏈狀烷氧基；異丙氧基、異丁氧基、第二丁氧基、第三丁氧基、異辛氧基等支鏈狀烷 氧基；環丙氧基、環戊氧基、環己氧基、環丙基甲氧基等環烷氧基；三氟甲基、五氟乙基、九氟丁基、三氟甲氧基等鹵代烷基或鹵代烷氧基；甲氧基羰基、乙氧基羰基、丙氧基羰基等烷氧基羰基等。該等之中，較佳為鹵素原子、碳原子數1~10之直鏈狀或支鏈狀之烷基、碳原子數3~10之環烷基、碳原子數1~10之直鏈狀或支鏈狀之烷氧基、碳原子數3~10之環烷氧基，尤佳為鹵素原子、碳原子數1~5之直鏈狀或支鏈狀之烷基、碳原子數1~5之直鏈狀或支鏈狀之烷氧基。 Examples of the "substituent" in the "substituted or unsubstituted nitrogen-containing aromatic heterocyclic group" represented by Ar 1 to Ar 5 in the general formulae (2) and (3) include a halogen atom and carbon. a linear or branched alkyl group having 1 to 10 atoms, a cycloalkyl group having 3 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, and a carbon number a cycloalkyloxy group of 3 to 10, a linear or branched haloalkyl group having 1 to 10 carbon atoms, a linear or branched haloalkoxy group having 1 to 10 carbon atoms, or an alkoxycarbonyl group; Wait. Specific examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. A straight-chain alkyl group; a branched alkyl group such as isopropyl, isobutyl, t-butyl, t-butyl or isooctyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. Cycloalkyl; linear alkoxy group such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy a branched alkoxy group such as isopropoxy group, isobutoxy group, second butoxy group, third butoxy group or isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, cyclohexyloxy group, a cycloalkyloxy group such as a cyclopropylmethoxy group; a halogenated alkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group or a trifluoromethoxy group; or a halogenated alkoxy group; a methoxycarbonyl group, an ethoxycarbonyl group, An alkoxycarbonyl group such as a propoxycarbonyl group. Among these, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a linear chain having 1 to 10 carbon atoms are preferable. Or a branched alkoxy group, a cycloalkyloxy group having 3 to 10 carbon atoms, particularly preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a carbon atom number of 1~ a linear or branched alkoxy group of 5.

通式(2)及(3)所表示之含氮化合物所具有之氮原子之數量較佳為4~8個，更佳為4~6個，尤佳為4個或5個。於可較佳地用於本發明之金屬錯合物中，通式(2)及(3)所表示之含氮化合物較佳為經由其所具有之氮原子中的3個以上之氮原子而配位於中心金屬上，尤佳為經由4個或5個氮原子而配位之四齒配位或五齒配位。 The nitrogen atom represented by the general formulae (2) and (3) preferably has 4 to 8 nitrogen atoms, more preferably 4 to 6 carbon atoms, and particularly preferably 4 or 5 nitrogen atoms. Among the metal complexes which can be preferably used in the present invention, the nitrogen-containing compounds represented by the general formulae (2) and (3) are preferably three or more nitrogen atoms among the nitrogen atoms thereof. It is located on the center metal, and is preferably a tetradentate coordination or a pentadentate coordination coordinated by 4 or 5 nitrogen atoms.

將通式(2)及(3)所表示之含氮化合物中的較佳之化合物之具體例示於以下，本發明並不限定於該等化合物。再者，即便於存在立體異構物之情形時，亦記載其平面結構式。 Specific examples of preferred compounds among the nitrogen-containing compounds represented by the general formulae (2) and (3) are shown below, and the present invention is not limited to these compounds. Further, even in the case where a stereoisomer is present, the planar structural formula is also described.

[化13] [Chemistry 13]

[化17] [化17]

形成本發明所使用之金屬錯合物之配位子可使用市售者，亦可使用藉由公知之方法(例如參照非專利文獻2、3)而合成者。 The ligand for forming the metal complex used in the present invention can be used commercially, or can be synthesized by a known method (for example, refer to Non-Patent Documents 2 and 3).

本發明所使用之金屬錯合物亦可含有使該金屬錯合物整體顯示電中性之陰離子。作為陰離子，並無特別限定，可列舉：氟化物離子、氯化物離子、溴化物離子、碘化物離子等鹵化物離子；硫化物離子、氧化物離子、氫氧化物離子、氫化物離子、亞硫酸離子、磷酸離子、氰化物離子、碳酸離子、碳酸氫離子、硫酸離子、硝酸離子、硫氰酸離子、四氟硼酸離子、六氟磷酸離子、六氟銻酸離子等無機酸離子；乙酸離子、三氟乙酸離子、三氟甲磺酸離子、四苯基硼酸離子、苯氧化物離子、吡啶甲酸及該等之衍生物之離子等有機酸離子等。其中，較佳為四氟硼酸離子、六氟磷酸離子、六氟銻酸離子，尤佳為六氟銻酸離子。又，該等陰離子亦可為兩種以上之混合陰離子。 The metal complex used in the present invention may also contain an anion which causes the metal complex to exhibit electrical neutrality as a whole. The anion is not particularly limited, and examples thereof include halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; sulfide ions, oxide ions, hydroxide ions, hydride ions, and sulfurous acid. Inorganic acid ions such as ions, phosphate ions, cyanide ions, carbonate ions, hydrogen carbonate ions, sulfate ions, nitrate ions, thiocyanate ions, tetrafluoroboric acid ions, hexafluorophosphate ions, hexafluoroantimonic acid ions; Organic acid ions such as trifluoroacetic acid ions, trifluoromethanesulfonate ions, tetraphenylboronic acid ions, phenoxide ions, picolinic acid, and ions of such derivatives. Among them, tetrafluoroboric acid ions, hexafluorophosphate ions, and hexafluoroantimonic acid ions are preferred, and hexafluoroantimonic acid ions are preferred. Further, the anions may be two or more kinds of mixed anions.

本發明所使用之金屬錯合物之合成方法並無特別限定，可藉由公知之方法(例如參照非專利文獻2)而合成。具體而言，可藉由於溶劑中使適當之配位子與氯化亞鐵等相應之金屬鹽反應而合成。 The method for synthesizing the metal complex used in the present invention is not particularly limited, and can be synthesized by a known method (for example, refer to Non-Patent Document 2). Specifically, it can be synthesized by reacting a suitable ligand with a corresponding metal salt such as ferrous chloride in a solvent.

本發明所使用之金屬錯合物之使用量相對於起始原料之金剛烷類，通常為0.001~2.0倍莫耳，較佳為0.005~0.5倍莫耳，更佳為0.01~0.1倍莫耳之範圍。於使用量較少之情形時，反應速度下降，因此欠佳，於使用量較多之情形時，使用大量金屬錯合物，就成本及反應時間等工業性觀點而言欠佳。 The amount of the metal complex used in the present invention is usually 0.001 to 2.0 times moles, preferably 0.005 to 0.5 times moles, more preferably 0.01 to 0.1 times moles, relative to the adamantane of the starting material. The scope. When the amount of use is small, the reaction rate is lowered, so that it is not preferable. When a large amount of metal is used, a large amount of metal complex is used, which is not preferable in terms of industrial viewpoints such as cost and reaction time.

本發明所使用之過氧化氫只要為作為試劑或工業用途而容易獲得者，則並無特別限制，較佳為使用5~60重量%之水溶液(過氧化氫水)。於過氧化氫水中之過氧化氫之濃度較低之情形時，反應溶液中的水之量變多，作為起始原料之金剛烷類之溶解度下降，導致反應性下降。另一方面，於過氧化氫之濃度較高之情形時，***等之危險性增大，因此欠佳。 The hydrogen peroxide used in the present invention is not particularly limited as long as it is easily obtained as a reagent or an industrial use, and it is preferred to use an aqueous solution (hydrogen peroxide water) of 5 to 60% by weight. When the concentration of hydrogen peroxide in the hydrogen peroxide water is low, the amount of water in the reaction solution increases, and the solubility of the adamantane as a starting material decreases, resulting in a decrease in reactivity. On the other hand, when the concentration of hydrogen peroxide is high, the risk of explosion or the like increases, which is not preferable.

本發明所使用之過氧化氫之添加量相對於起始原料之金剛烷類，通常為0.5~20倍莫耳，較佳為1.0~15倍莫耳，更佳為1.2~12倍莫耳之範圍。於過氧化氫之添加量較少之情形時，殘存大量之未反應之原料或作為反應中間物之金剛烷單醇類、金剛烷二醇類，金剛烷三醇類之選擇性及產率下降。另一方面，於過氧化氫之添加量較多之情形時，會副生於目標金剛烷三醇中進一步導入羥基之金剛烷四醇類等金剛烷多元醇類，金剛烷三醇類之選擇性及產率同樣會下降。 The amount of hydrogen peroxide used in the present invention is usually 0.5 to 20 moles, preferably 1.0 to 15 moles, more preferably 1.2 to 12 moles, per mole of the adamantane of the starting material. range. When the amount of hydrogen peroxide added is small, the selectivity and yield of adamantane triols remaining in a large amount of unreacted raw materials or adamantane monools as a reaction intermediate, adamantanediols, and adamantane are decreased. . On the other hand, when the amount of hydrogen peroxide added is large, the adamantane polyol such as adamantane tetraol which is further introduced into the target adamantane triol to introduce a hydroxyl group, and the choice of adamantane triol Sex and productivity will also decline.

於本發明中，於使上述通式(1)所表示之金剛烷類於溶劑中且於金屬錯合物之存在與過氧化氫反應時，較佳為進而存在有機酸。如下所述，若反應系統之pH值大於6，則有引起過氧化氫之分解之虞，藉由於反應系統中存在有機酸，可將反應系統之pH值調整為6以下。本發明所使用之有機酸只要與水之相溶性較高，且於本發明之反應條件下為惰性，則並無特別限制。作為此種有機酸，可列舉：甲酸、乙酸、丙酸、草酸、琥珀酸等脂肪族羧酸；苯甲酸、鄰苯二甲酸、間苯二甲酸等芳香族羧酸；乳酸、檸檬酸、水楊酸等羥酸等。該等之中，較佳為脂肪族羧酸或芳香族羧酸，就獲得之容易性、價格方面而言，尤佳為乙酸。該等有機酸可單獨使用，亦可混合兩種以上而使用。有機酸之使用量相對於起始原料之金剛烷類，通常為0.1~10倍莫耳，較佳為0.3~8.0倍莫耳，更佳為0.5~6.0倍莫耳之範圍。 In the present invention, when the adamantane represented by the above formula (1) is allowed to react with hydrogen peroxide in a solvent and in the presence of a metal complex, an organic acid is further present. As described below, if the pH of the reaction system is more than 6, there is a possibility of causing decomposition of hydrogen peroxide, and the pH of the reaction system can be adjusted to 6 or less by the presence of an organic acid in the reaction system. The organic acid used in the present invention is not particularly limited as long as it has high compatibility with water and is inert under the reaction conditions of the present invention. Examples of such an organic acid include aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, and succinic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, and isophthalic acid; lactic acid, citric acid, and water. Hydroxamic acid such as salicylic acid. Among these, an aliphatic carboxylic acid or an aromatic carboxylic acid is preferable, and acetic acid is especially preferable in terms of availability and price. These organic acids may be used singly or in combination of two or more. The amount of the organic acid used is usually 0.1 to 10 moles, preferably 0.3 to 8.0 moles, more preferably 0.5 to 6.0 moles per mole of the adamantane of the starting material.

本發明所使用之溶劑可單獨使用水或有機溶劑、或者混合使用，較佳為水/有機溶劑之混合溶液。作為有機溶劑，只要為相對於本發明之氧化反應為惰性之溶劑，則並無特別限制，較佳為與水之相溶性及金屬錯合物之溶解性較高者。於與水之相溶性較低之情形時，反應溶液分離成2相，導致反應速度下降。又，於金屬錯合物之溶解性較低之情形時，反應速度亦下降。作為可較佳地用於本發明之有機溶劑，可列舉：甲醇、乙醇、丙醇、異丙醇等醇；乙腈、苯甲腈等腈 化合物；四氫呋喃；丙酮等水溶性有機溶劑。該等之中，尤佳為乙腈。該等有機溶劑可單獨使用，亦可混合兩種以上之溶劑而使用。有機溶劑相對於起始原料之金剛烷類1重量份，通常於0.1~200重量份之範圍內使用，較佳為以10~100重量份之比率使用。又，於製成水/有機溶劑之混合溶液而使用之情形時，較佳為將水(包含過氧化氫水中之水)與有機溶劑之混合比以重量比計設為1：2~1：100之範圍內而使用。 The solvent used in the present invention may be used singly or in combination with water or an organic solvent, preferably a mixed solution of water/organic solvent. The organic solvent is not particularly limited as long as it is inert to the oxidation reaction of the present invention, and it is preferred that the compatibility with water and the solubility of the metal complex are high. When the compatibility with water is low, the reaction solution separates into two phases, resulting in a decrease in the reaction rate. Further, when the solubility of the metal complex is low, the reaction rate also decreases. Examples of the organic solvent which can be preferably used in the present invention include alcohols such as methanol, ethanol, propanol and isopropanol; and nitriles such as acetonitrile and benzonitrile. a compound; tetrahydrofuran; a water-soluble organic solvent such as acetone. Among these, acetonitrile is preferred. These organic solvents may be used singly or in combination of two or more kinds of solvents. The organic solvent is usually used in an amount of from 0.1 to 200 parts by weight, preferably from 10 to 100 parts by weight, based on 1 part by weight of the adamantane of the starting material. Further, in the case of being used as a mixed solution of water/organic solvent, it is preferred to set the mixing ratio of water (including water in hydrogen peroxide water) to the organic solvent to be 1:2 to 1: by weight ratio: Used within the scope of 100.

作為本發明之氧化反應之反應溫度，通常為0~100℃，較佳為0~80℃之範圍內，更佳為0~50℃，尤佳為15~40℃之範圍。於反應溫度較低之情形時，反應速度下降，於較高之情形時，由於過氧化氫之分解或副反應而導致金剛烷三醇類之選擇性及產率下降。 The reaction temperature of the oxidation reaction of the present invention is usually 0 to 100 ° C, preferably 0 to 80 ° C, more preferably 0 to 50 ° C, and particularly preferably 15 to 40 ° C. When the reaction temperature is low, the reaction rate is lowered, and at a higher level, the selectivity and yield of the adamantane triol are lowered due to the decomposition or side reaction of hydrogen peroxide.

本發明之氧化反應之反應時間係通常進行1分鐘~50小時。 The reaction time of the oxidation reaction of the present invention is usually carried out for 1 minute to 50 hours.

反應液之pH值並無特別限定，於鹼性條件下促進過氧化氫之分解，引起有機酸之中和，因此較佳為於酸性~中性條件下進行，更佳為於酸性條件下進行，尤佳為於pH值6以下進行。 The pH of the reaction liquid is not particularly limited, and the decomposition of hydrogen peroxide is promoted under alkaline conditions to cause neutralization of the organic acid. Therefore, it is preferably carried out under acidic to neutral conditions, and more preferably under acidic conditions. It is especially preferred to carry out the pH below 6.

本發明中使用之反應容器並無特別限定，可使用公知之具備攪拌機之反應容器而進行反應。試劑之添加順序並無特別限制，較佳為首先將成為起始原料之金剛烷類、作為觸媒之金屬錯合物(及較佳之有機酸)溶解於溶劑中，於其中添加過氧化氫(過氧化氫水)。過氧化氫(過氧化氫水)之添加方法並無特別限制，為了防止由反應熱所致的急劇之溫度上升，較佳為視需要利用溶劑稀釋後，一面藉由滴加等調整添加速度一面進行添加。 The reaction container used in the present invention is not particularly limited, and a reaction can be carried out using a known reaction vessel equipped with a stirrer. The order of addition of the reagent is not particularly limited, and it is preferred to first dissolve the adamantane as a starting material, a metal complex as a catalyst (and preferably an organic acid) in a solvent, and add hydrogen peroxide thereto ( Hydrogen peroxide water). The method of adding hydrogen peroxide (hydrogen peroxide water) is not particularly limited, and in order to prevent an abrupt temperature rise due to the heat of reaction, it is preferred to adjust the addition rate by dripping or the like after dilution with a solvent as needed. Add it.

金屬錯合物(及較佳之有機酸)、過氧化氫(過氧化氫水)可一次添加總量，亦可逐次少量地分複數次添加。即便於一次添加總量之情形時，過氧化氫(過氧化氫水)亦較佳為藉由滴加而添加總量。又，於逐 次少量地分複數次添加之情形時，添加量及添加次數並無特別限制，較佳為一面利用各種機器分析等確認反應之進展，一面以所需次數添加適當之量。 The metal complex (and preferably the organic acid) and the hydrogen peroxide (hydrogen peroxide) may be added in one portion at a time, or may be added in small portions in small portions. That is, in the case where it is convenient to add the total amount at a time, hydrogen peroxide (hydrogen peroxide water) is also preferably added in a total amount by dropping. Again When the amount of addition and the number of additions are not particularly limited, the amount of addition and the number of additions are not particularly limited, and it is preferred to add an appropriate amount to the required number of times while confirming the progress of the reaction by various machine analysis or the like.

確認反應之進展時之取樣可利用公知之方法進行，於採取之反應液中存在不溶份(金剛烷類、金剛烷醇類等)之情形時，較佳為藉由添加適當之溶劑而使不溶份溶解後進行分析。作為可使用之溶劑，只要為與反應溶液之相溶性較高，且所含之各種成分之溶解度較高者，則並無特別限制，例如可列舉：水、甲醇、乙醇、丙醇、異丙醇、丁醇、乙腈、四氫呋喃、丙酮、乙酸乙酯、氯仿等。該等之中，尤佳為水、丁醇、乙腈、乙酸乙酯、氯仿。該等溶劑可單獨使用，亦可混合兩種以上而使用。於使用與反應溶液之相溶性較低之溶劑之情形時，取樣液分離成2相，無法正確地進行分析。又，於使用反應液中所含之各種成分之溶解度較低的溶劑之情形時，為了避免難溶成分之析出，亦需要大量之溶劑，其結果，取樣液整體之濃度下降，分析變得困難。 When the progress of the reaction is confirmed, sampling can be carried out by a known method. When an insoluble fraction (adamantane, amantadine, etc.) is present in the reaction liquid to be used, it is preferred to insoluble by adding an appropriate solvent. The fractions were dissolved and analyzed. The solvent to be used is not particularly limited as long as it has high compatibility with the reaction solution and the solubility of various components contained therein is high, and examples thereof include water, methanol, ethanol, propanol, and isopropyl alcohol. Alcohol, butanol, acetonitrile, tetrahydrofuran, acetone, ethyl acetate, chloroform, and the like. Among these, water, butanol, acetonitrile, ethyl acetate, and chloroform are particularly preferred. These solvents may be used singly or in combination of two or more. When a solvent having a low compatibility with the reaction solution is used, the sample liquid is separated into two phases, and the analysis cannot be performed correctly. Further, when a solvent having a low solubility of various components contained in the reaction liquid is used, a large amount of solvent is required in order to avoid precipitation of a poorly soluble component, and as a result, the concentration of the entire sample liquid is lowered, and analysis becomes difficult. .

於本發明中，用以確認反應之進展之分析法並無特別限制，可使用公知之分析法。作為分析法，較佳為無需特別之預處理而能夠進行定性且定量之分析的方法，例如較佳為氣相層析法(GC)分析、高效液相層析法(HPLC)分析等機器分析。GC分析或HPLC分析所使用之管柱並無特別限制，由於本發明之目標物的金剛烷三醇類為高極性且高沸點之化合物，因此較佳為與此種化合物對應之管柱，例如於為GC分析之情形時，較佳為財團法人化學物質評價研究機構公司製造之G-250管柱等。 In the present invention, the analysis method for confirming the progress of the reaction is not particularly limited, and a known analytical method can be used. As the analysis method, a method capable of performing qualitative and quantitative analysis without special pretreatment is preferable, and for example, gas chromatography (GC) analysis, high performance liquid chromatography (HPLC) analysis, and the like are preferably performed. . The column to be used for the GC analysis or the HPLC analysis is not particularly limited, and since the adamantane triol of the object of the present invention is a compound having high polarity and high boiling point, it is preferably a column corresponding to the compound, for example, In the case of the GC analysis, it is preferably a G-250 column manufactured by a chemical substance evaluation research institute company.

氧化反應結束後，視需要亦可進行藉由還原劑之未反應之過氧化氫之分解或使用鹼之中和。作為還原劑，可列舉：硼氫化鈉、氫化鋁鋰等金屬氫化物；亞硫酸鉀、亞硫酸銨、亞硫酸氫鈉等亞硫酸鹽； 肼、草酸等，尤佳為亞硫酸氫鈉。又，作為中和所使用之鹼，可列舉：氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鋇等金屬氫氧化物；碳酸鈉、碳酸鉀、碳酸鈣、碳酸銨、碳酸鎂、碳酸氫鈉等碳酸鹽；三乙胺、三甲胺等胺類；四甲基氫氧化銨等烷基氫氧化銨，尤佳為碳酸鈉、碳酸氫鈉。還原劑或鹼可直接添加，亦可製成溶液而添加。 After completion of the oxidation reaction, decomposition of unreacted hydrogen peroxide by a reducing agent or neutralization with a base may be carried out as needed. Examples of the reducing agent include metal hydrides such as sodium borohydride and lithium aluminum hydride; sulfites such as potassium sulfite, ammonium sulfite, and sodium hydrogen sulfite; Helium, oxalic acid, etc., especially sodium hydrogen sulfite. Further, examples of the base used for the neutralization include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide; sodium carbonate, potassium carbonate, calcium carbonate, ammonium carbonate, magnesium carbonate, and carbonic acid. A carbonate such as sodium hydrogen; an amine such as triethylamine or trimethylamine; an alkyl ammonium hydroxide such as tetramethylammonium hydroxide; and more preferably sodium carbonate or sodium hydrogencarbonate. The reducing agent or the base may be added directly or may be added as a solution.

於本發明中，可以高選擇性且高產率獲得金剛烷三醇類，但有於反應結束後之溶液中存在未反應之金剛烷類及少量之金剛烷單醇類及/或金剛烷二醇類等之情形。於此種情形時，可使用公知之分離純化法自反應結束後之溶液中提取金剛烷三醇類。作為公知之分離純化法，可列舉：過濾、濃縮、蒸餾、萃取、晶析、再結晶、管柱層析法等，亦可組合該等而使用。 In the present invention, adamantane triols can be obtained with high selectivity and high yield, but there are unreacted adamantane and a small amount of adamantane monool and/or adamantanediol in the solution after the reaction is completed. The situation of classes, etc. In this case, the adamantane triol can be extracted from the solution after completion of the reaction by a known separation and purification method. The known separation and purification method may be, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like, or may be used in combination.

具體而言，可藉由如下方法進行分離純化。作為本發明之起始原料之金剛烷類及金剛烷單醇類容易溶解於非水溶性有機溶劑中，具有兩個以上之羥基之金剛烷醇類(金剛烷二醇類、金剛烷三醇類等)容易溶解於水或水溶性有機溶劑中。利用該溶解性之差異，首先，自反應結束後之反應液中分離金剛烷二醇類及/或金剛烷三醇類。即，藉由於反應液中添加非水溶性有機溶劑進行分液操作，而於有機層萃取起始原料之金剛烷類及/或金剛烷單醇類，又，於水層萃取金剛烷二醇類及/或金剛烷三醇類。作為此處所使用之非水溶性有機溶劑，可列舉：己烷、甲苯、乙酸乙酯、丁醇、戊醇、己醇、氯仿、二氯甲烷等，就極性及與水之分離性之觀點而言，較佳為己烷、甲苯。繼而，藉由濃縮水層而獲得金剛烷二醇類及/或金剛烷三醇類之粗產物，但有時會混入有無機鹽。於該情形時，可視需要藉由熱醇萃取或離子交換處理等去除無機鹽。進而，藉由對所得之金剛烷二醇類及/或金剛烷三醇類之粗產物進行再結晶，可純度良好地獲得目標物之金剛烷三醇類。作為再結晶所使用之溶劑，可列舉：水、甲醇、乙醇、丙醇、 2-丙醇、1-丁醇、2-丁醇、己醇、乙腈、己烷、環己烷、丙酮、乙酸乙酯、四氫呋喃、氯仿、二氯甲烷、甲苯等，尤佳為水、甲醇、乙醇、丙酮、乙酸乙酯、氯仿。該等溶劑可單獨使用，亦可混合兩種以上而使用。 Specifically, separation and purification can be carried out by the following method. Adamantane and adamantane monool which are starting materials of the present invention are easily dissolved in a water-insoluble organic solvent, and adamantyl alcohols having two or more hydroxyl groups (adamantanediols, adamantanetriols) Equivalent to being easily dissolved in water or a water-soluble organic solvent. Using this difference in solubility, first, adamantanediols and/or adamantanetriols are separated from the reaction liquid after completion of the reaction. That is, by adding a water-insoluble organic solvent to the reaction liquid to perform a liquid separation operation, the adamantane and/or adamantane monool of the starting material are extracted in the organic layer, and the adamantanediol is extracted in the aqueous layer. And / or adamantane triols. Examples of the water-insoluble organic solvent used herein include hexane, toluene, ethyl acetate, butanol, pentanol, hexanol, chloroform, and dichloromethane. From the viewpoints of polarity and separation from water, In other words, hexane or toluene is preferred. Then, a crude product of adamantanediol and/or adamantanetriol is obtained by concentrating the aqueous layer, but an inorganic salt may be mixed in some cases. In this case, the inorganic salt may be removed by hot alcohol extraction or ion exchange treatment or the like as needed. Further, by recrystallizing the obtained crude product of adamantanediol and/or adamantanetriol, the adamantanetriol of the target can be obtained with good purity. Examples of the solvent used for recrystallization include water, methanol, ethanol, and propanol. 2-propanol, 1-butanol, 2-butanol, hexanol, acetonitrile, hexane, cyclohexane, acetone, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane, toluene, etc., especially water, methanol , ethanol, acetone, ethyl acetate, chloroform. These solvents may be used singly or in combination of two or more.

[實施例] [Examples]

以下，藉由實施例對本發明進行具體說明，本發明並不限定於該等實施例。 Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples.

[分析條件] [Analysis conditions]

氧化反應之確認及產物之確認係藉由GC分析而進行。分析條件係如下所示。管柱：化學物質評價研究機構製造之G-250、1.2mm×40m×1.0μm；管柱溫度：於120℃下保持5分鐘後，以10℃/min升溫至200℃，於200℃下保持15分鐘；注入口溫度：300℃；檢測器(氫焰離子化檢測器)溫度：280℃；載氣：氦；流量：17ml/min。 Confirmation of the oxidation reaction and confirmation of the product were carried out by GC analysis. The analysis conditions are as follows. Pipe column: G-250, 1.2mm × 40m × 1.0μm manufactured by chemical substance evaluation research institute; column temperature: after maintaining for 5 minutes at 120 ° C, the temperature is raised to 200 ° C at 10 ° C / min, and maintained at 200 ° C 15 minutes; inlet temperature: 300 ° C; detector (hydrogen ionization detector) temperature: 280 ° C; carrier gas: helium; flow: 17 ml / min.

[實施例1] [Example 1] [鐵錯合物(C-2)之合成] [Synthesis of iron complex (C-2)]

於氮氣環境下，於安裝有攪拌機、溫度計、冷卻器之反應容器中添加(S,S)-2,2'-二吡咯啶D-酒石酸鹽1.07g、水10ml、二氯甲烷10ml，於水冷條件下一面攪拌一面添加氫氧化鈉0.88g。其後，於室溫下添加2-氯甲基吡啶鹽酸鹽1.19g並攪拌8小時。對反應液進行分液，利用飽和食鹽水20ml將所得之有機層洗淨後，利用無水硫酸鎂進行乾燥，餾去溶劑，藉此獲得粗產物1.03g。利用管柱層析法(載體：NH矽膠、溶析液：甲苯/乙酸乙酯)將粗產物純化而獲得配位子(L-8)0.60g(產率59%)。 Add (S,S)-2,2'-dipyrrolidine D-tartrate 1.07 g, 10 ml of water, 10 ml of dichloromethane to a water-cooled reaction vessel equipped with a stirrer, a thermometer, and a cooler under a nitrogen atmosphere. Under the conditions, 0.88 g of sodium hydroxide was added while stirring. Thereafter, 1.19 g of 2-chloromethylpyridine hydrochloride was added at room temperature and stirred for 8 hours. The reaction mixture was separated, and the obtained organic layer was washed with 20 ml of brine, dried over anhydrous magnesium sulfate, and evaporated. The crude product was purified by column chromatography (carrier: NH silica gel, eluting solvent: toluene/ethyl acetate) to give the compound (L-8) 0.60 g (yield 59%).

於氮氣環境下，於反應容器中添加配位子(L-8)1.41g、氯化鐵(II)四水合物0.92g、乙腈30ml，於室溫下攪拌7小時。於反應液中添加二異丙醚20ml並攪拌30分鐘而使金屬錯合物析出。使用二異丙醚 20ml將利用傾析法去除溶劑所得之結晶洗淨兩次並進行乾燥，藉此獲得鐵錯合物(C-1)1.64g(產率71%)。 To the reaction vessel, 1.41 g of a ligand (L-8), 0.92 g of iron (II) chloride tetrahydrate, and 30 ml of acetonitrile were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. 20 ml of diisopropyl ether was added to the reaction liquid, and the mixture was stirred for 30 minutes to precipitate a metal complex. Diisopropyl ether 20 ml of the crystal obtained by removing the solvent by decantation was washed twice and dried, whereby 1.64 g (yield 71%) of the iron complex (C-1) was obtained.

於氮氣環境下，於遮光反應容器中添加鐵錯合物(C-1)1.64g、六氟銻(V)酸銀2.55g、乙腈50ml並於室溫下攪拌6小時。藉由使用波來鐵過濾反應液而去除不溶份。自濾液中餾去溶劑後，將所得之固體溶解於乙腈中，使用孔徑0.2μm之注射式過濾器再次對不溶份進行過濾分離而餾去溶劑。藉由反覆進行3次該純化操作而獲得下述結構式(C-2)所表示之鐵錯合物2.75g(產率96%)。 To the light-shielding reaction vessel, 1.64 g of iron complex (C-1), 2.55 g of silver hexafluoroantimony (V), and 50 ml of acetonitrile were added to the light-shielding reaction vessel, and the mixture was stirred at room temperature for 6 hours. The insoluble matter was removed by filtering the reaction solution using a wave of iron. After distilling off the solvent from the filtrate, the obtained solid was dissolved in acetonitrile, and the insoluble portion was again subjected to filtration separation using a syringe filter having a pore size of 0.2 μm to distill off the solvent. 2.75 g (yield 96%) of the iron complex represented by the following structural formula (C-2) was obtained by repeating this purification operation three times.

[實施例2] [Embodiment 2] [鐵錯合物(C-4)之合成] [Synthesis of iron complex (C-4)]

於氮氣環境下，於安裝有攪拌機、溫度計、冷卻器之反應容器中添加吡啶-2-甲醛9.02g、N,N'-二甲基伸乙基-1,2-二胺3.71g、二氯甲烷300ml，於室溫下進行攪拌。分4次且每次歷經15分鐘添加三乙醯氧基硼氫化鈉25.0g後，於室溫下攪拌12小時。於反應液中添加飽和碳酸氫鈉水溶液100ml並進行分液，利用飽和食鹽水100ml將所得之有機層洗淨後，利用無水硫酸鎂進行乾燥，餾去溶劑，藉此獲得粗產物9.82g。利用管柱層析法(載體：NH矽膠，溶析液：氯仿/乙酸乙酯)將粗產物純化而獲得配位子(L-1)4.63g(產率41%)。 In a reaction vessel equipped with a stirrer, a thermometer, and a cooler, 9.02 g of pyridine-2-carbaldehyde, 3.71 g of N,N'-dimethylethylidene-1,2-diamine, and dichloride were added under a nitrogen atmosphere. Methane (300 ml) was stirred at room temperature. After adding 25.0 g of sodium triethoxysulfonate hydride for 4 times and every 15 minutes, it was stirred at room temperature for 12 hours. 100 ml of a saturated aqueous sodium hydrogencarbonate solution was added to the reaction mixture, and the obtained organic layer was washed with 100 ml of a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvent was evaporated. The crude product was purified by column chromatography (yield: NH EtOAc, EtOAc: EtOAc/ethyl acetate) to afford (yield: 41%).

於氮氣環境下，於反應容器中添加配位子(L-1)4.63g、氯化鐵(II)四水合物3.40g、乙腈100ml，於室溫攪拌7小時。於反應液中添加二異丙醚100ml並攪拌30分鐘，使金屬錯合物析出。使用二異丙醚50ml將利用傾析法去除溶劑所得之結晶洗淨兩次並進行乾燥，藉此獲得鐵錯合物(C-3)6.21g(產率76%)。 Under a nitrogen atmosphere, 4.63 g of a ligand (L-1), 3.40 g of iron(II) chloride tetrahydrate, and 100 ml of acetonitrile were added to the reaction vessel, and the mixture was stirred at room temperature for 7 hours. 100 ml of diisopropyl ether was added to the reaction liquid, and the mixture was stirred for 30 minutes to precipitate a metal complex. The crystal obtained by removing the solvent by decantation was washed twice with 50 ml of diisopropyl ether and dried, whereby 6.21 g (yield 76%) of the iron complex (C-3) was obtained.

於氮氣環境下，於遮光反應容器中添加鐵錯合物(C-3)6.18g、六氟銻(V)酸銀10.66g、乙腈200ml，於室溫下攪拌6小時。藉由使用波來鐵過濾反應液而去除不溶份。自濾液中餾去溶劑後，將所得之固體 溶解於乙腈中，使用孔徑0.2μm之注射式過濾器再次將不溶份過濾分離而餾去溶劑。藉由反覆進行3次該純化操作而獲得下述結構式(C-4)所表示之鐵錯合物10.39g(產率95%)。 Under a nitrogen atmosphere, 6.18 g of an iron complex (C-3), 10.66 g of silver hexafluoroantimony (V), and 200 ml of acetonitrile were added to a light-shielding reaction vessel, and the mixture was stirred at room temperature for 6 hours. The insoluble matter was removed by filtering the reaction solution using a wave of iron. After distilling off the solvent from the filtrate, the resulting solid The solvent was dissolved in acetonitrile, and the insoluble fraction was again separated by filtration using a syringe filter having a pore size of 0.2 μm to distill off the solvent. By repeating this purification operation three times, 10.39 g (yield 95%) of the iron complex represented by the following structural formula (C-4) was obtained.

[實施例3] [Example 3] [金剛烷三醇之合成] [Synthesis of adamantane triol]

於反應容器中添加金剛烷4.00g(29.4mmol)、乙酸0.882g(14.7mmol)、作為觸媒之實施例1中合成之鐵錯合物(C-2)274mg(0.294mmol)、乙腈180ml，於室溫下一面攪拌一面歷經30分鐘將乙腈120ml與30%過氧化氫水4.00g(過氧化氫為35.3mmol)之混合液滴加至燒瓶內。其後，每30分添加鐵錯合物274mg(0.294mmol)、乙酸0.882g(14.7mmol)、30%過氧化氫水4.00g(過氧化氫為35.3mmol)，共計添加9次。期間，藉由GC分析一面確認反應一面進行。進行追加直至最終合計使用量分別成為鐵錯合物2.74g(相對於基質，為0.1倍莫耳)、乙酸8.82g(相對於基質，為5.0倍莫耳)、30%過氧化氫水40.0g(相對於基質，過氧化氫為12倍莫耳)，進而攪拌一小時後結束反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷單醇：0.0%、金剛烷二醇：4.6%、1,3,5-金剛烷三醇：72%。將結果匯總示於表1中。 4.00 g (29.4 mmol) of adamantane, 0.882 g (14.7 mmol) of acetic acid, 274 mg (0.294 mmol) of the iron complex (C-2) synthesized in Example 1 as a catalyst, and 180 ml of acetonitrile were added to the reaction vessel. A mixture of 120 ml of acetonitrile and 4.00 g of 30% hydrogen peroxide water (hydrogen peroxide 35.3 mmol) was added dropwise to the flask over 30 minutes while stirring at room temperature. Thereafter, 274 mg (0.294 mmol) of iron complex, 0.882 g (14.7 mmol) of acetic acid, and 4.00 g of hydrogen peroxide (35.3 mmol of hydrogen peroxide) were added every 30 minutes for 9 times. During the period, the reaction was confirmed by GC analysis. The addition was carried out until the final total amount of use was 2.74 g of iron complex (0.1 mol% relative to the substrate), 8.82 g of acetic acid (5.0 mols relative to the matrix), and 300.0 g of 30% hydrogen peroxide water. (12 moles of hydrogen peroxide relative to the substrate), and the reaction was terminated after stirring for one hour. The results of GC analysis at the end of the reaction were adamantane monol: 0.0%, adamantanediol: 4.6%, and 1,3,5-adamantane triol: 72% in terms of peak area ratio. The results are summarized in Table 1.

於反應結束後之反應液中添加水500ml，添加5%亞硫酸氫鈉水溶液而使過剩之過氧化氫分解，使用飽和碳酸氫鈉水溶液中和反應液。添加甲苯300ml進行分液操作後，提取水層，利用甲苯100ml將所提取之水層洗淨。藉由將水層濃縮、乾燥而獲得金剛烷三醇之粗產物121.07g。於所得之粗產物中添加甲醇150ml並加熱，於60℃下進行攪拌，其後進行熱過濾而去除不溶物。於藉由將濾液濃縮而獲得之結晶中添加甲醇100ml，反覆進行該操作而獲得結晶。將所得之結晶溶解於水150ml中後，將所得之溶液通入填充有強酸性陽離子交換樹脂100ml之管柱中。針對將通液後之溶液濃縮而獲得之結晶4.22g，進行藉由使用甲醇/氯仿之再結晶的純化，獲得2.38g(產率44%)之1,3,5-金剛烷三醇之白色結晶(純度98%)。 500 ml of water was added to the reaction liquid after completion of the reaction, and a 5% aqueous solution of sodium hydrogen sulfite was added to decompose excess hydrogen peroxide, and the reaction liquid was neutralized with a saturated aqueous solution of sodium hydrogencarbonate. After adding 300 ml of toluene to carry out a liquid separation operation, the aqueous layer was extracted, and the extracted aqueous layer was washed with 100 ml of toluene. The crude product of adamantanetriol was obtained by concentrating and drying the aqueous layer to 121.07 g. To the obtained crude product, 150 ml of methanol was added and heated, and the mixture was stirred at 60 ° C, and then subjected to hot filtration to remove insoluble matter. To the crystal obtained by concentrating the filtrate, 100 ml of methanol was added, and the operation was repeated to obtain crystals. After dissolving the obtained crystal in 150 ml of water, the resulting solution was passed through a column packed with 100 ml of a strongly acidic cation exchange resin. 4.22 g of the crystal obtained by concentrating the solution after the liquid passage was subjected to purification by recrystallization using methanol/chloroform to obtain 2.38 g (yield: 44%) of white of 1,3,5-adamantane triol. Crystallization (purity 98%).

[實施例4] [Example 4]

除使用1,3-金剛烷二醇代替金剛烷作為起始物質以外，於與實施例3相同之條件下進行反應。進行追加直至最終合計使用量分別成為觸媒1.34g(相對於基質，為0.06倍莫耳)、乙酸4.28g(相對於基質，為3.0倍莫耳)、30%過氧化氫水19.4g(相對於基質，過氧化氫為7.2倍莫耳)，進而攪拌一小時後結束反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷二醇：9.0%、1,3,5-金剛烷三醇：86%。將結果匯總示於表1中。 The reaction was carried out under the same conditions as in Example 3 except that 1,3-adamantanediol was used instead of adamantane as a starting material. Addition until the final total amount of use is 1.34 g of catalyst (0.06 mols relative to the matrix), 4.28 g of acetic acid (3.0 mols relative to the matrix), and 19.4 g of 30% hydrogen peroxide (relatively) In the matrix, hydrogen peroxide was 7.2 moles, and the reaction was completed after stirring for one hour. The results of GC analysis at the end of the reaction were adamantanediol: 9.0%, 1,3,5-adamantane triol: 86% in terms of peak area ratio. The results are summarized in Table 1.

[實施例5] [Example 5]

於反應容器中添加金剛烷4.00g(29.4mmol)、乙酸0.882g(14.7mmol)、作為觸媒之實施例1中合成之鐵錯合物(C-2)822mg(0.882mmol)、乙腈150ml，於室溫下一面攪拌一面歷經120分鐘將乙腈150ml與30%過氧化氫水33.3g(過氧化氫為294mmol)之混合液滴加至燒瓶內。其後，進而攪拌一小時，結束反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷單醇：0.0%、金剛烷二醇：5.9%、 1,3,5-金剛烷三醇：80%。將結果匯總示於表1中。 4.00 g (29.4 mmol) of adamantane, 0.882 g (14.7 mmol) of acetic acid, 822 mg (0.882 mmol) of iron complex (C-2) synthesized in Example 1 as a catalyst, and 150 ml of acetonitrile were added to the reaction vessel. A mixture of 150 ml of acetonitrile and 33.3 g of 30% hydrogen peroxide water (hydrogen peroxide: 294 mmol) was added dropwise to the flask over 120 minutes while stirring at room temperature. Thereafter, the mixture was further stirred for one hour to complete the reaction. The results of GC analysis at the end of the reaction were adamantane monool: 0.0%, adamantanediol: 5.9%, in terms of peak area ratio, 1,3,5-adamantane triol: 80%. The results are summarized in Table 1.

[實施例6] [Embodiment 6]

除使用實施例2中合成之鐵錯合物(C-4)代替鐵錯合物(C-2)作為觸媒以外，於與實施例3相同之條件下進行反應。進行追加直至最終合計使用量分別成為觸媒2.94g(相對於基質，為0.1倍莫耳)、乙酸8.82g(相對於基質，為5.0倍莫耳)、30%過氧化氫水40.0g(相對於基質，過氧化氫為12倍莫耳)，進而攪拌一小時後結束反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷單醇：0.0%、金剛烷二醇：9.8%、1,3,5-金剛烷三醇：41%。將結果匯總示於表1中。 The reaction was carried out under the same conditions as in Example 3, except that the iron complex (C-4) synthesized in Example 2 was used instead of the iron complex (C-2) as a catalyst. Addition until the final total amount of use is 2.94 g of catalyst (0.1 times mole relative to the substrate), 8.82 g of acetic acid (5.0 times mole relative to the substrate), and 40.0 g of 30% hydrogen peroxide water (relatively In the matrix, hydrogen peroxide was 12 times moles, and the reaction was terminated after stirring for one hour. The results of GC analysis at the end of the reaction were adamantane monool: 0.0%, adamantanediol: 9.8%, and 1,3,5-adamantane triol: 41% in terms of peak area ratio. The results are summarized in Table 1.

[比較例1] [Comparative Example 1]

使用次氯酸鈉(10%水溶液)代替過氧化氫作為氧化劑，且不使用有機酸(乙酸)，除此以外，於與實施例5相同之條件下進行氧化反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷單醇：25%、金剛烷二醇：4.7%、1,3,5-金剛烷三醇：1.9%。將結果匯總示於表1中。 The oxidation reaction was carried out under the same conditions as in Example 5 except that sodium hypochlorite (10% aqueous solution) was used instead of hydrogen peroxide as the oxidizing agent, and the organic acid (acetic acid) was not used. The results of GC analysis at the end of the reaction were adamantane monool: 25%, adamantanediol: 4.7%, and 1,3,5-adamantane triol: 1.9% in terms of peak area ratio. The results are summarized in Table 1.

[比較例2] [Comparative Example 2]

使用次氯酸鈉(10%水溶液)作為氧化劑，使用乙酸作為有機酸，使用實施例2中合成之鐵錯合物(C-4)作為觸媒，將相對於基質之氧化劑、有機酸、及觸媒之使用量分別設為1.2倍莫耳、0.5倍莫耳、及0.05倍莫耳，除此以外，於與實施例3相同之條件下進行氧化反應。與實施例3相比，反應之進展較慢，因此不進行第二次以後之氧化劑等之追加而結束反應。反應結束時之GC分析之結果以波峰面積比計為金剛烷單醇：16%、金剛烷二醇：3.3%、1,3,5-金剛烷三醇：0.0%。將結果匯總示於表1中。 Using sodium hypochlorite (10% aqueous solution) as an oxidizing agent and acetic acid as an organic acid, using the iron complex (C-4) synthesized in Example 2 as a catalyst, an oxidizing agent, an organic acid, and a catalyst are used with respect to the substrate. The oxidation reaction was carried out under the same conditions as in Example 3 except that the amounts used were 1.2 times moles, 0.5 times moles, and 0.05 times moles. Since the progress of the reaction was slower than in Example 3, the reaction was terminated without adding the oxidizing agent or the like after the second time. The results of GC analysis at the end of the reaction were adamantane monool: 16%, adamantanediol: 3.3%, and 1,3,5-adamantane triol: 0.0% in terms of peak area ratio. The results are summarized in Table 1.

根據表1之結果可知，於使用過氧化氫作為氧化劑之實施例3~6中，可以高選擇性且高產率獲得目標之金剛烷三醇，相對於此，於使用次氯酸鈉作為氧化劑之比較例1及2中，幾乎無法獲得金剛烷三醇。又，根據實施例3及實施例5之結果可知，分批添加觸媒、有機酸及氧化劑之情形、一次添加總量之情形均可以高選擇性且高產率獲得金剛烷三醇。 According to the results of Table 1, in Examples 3 to 6 in which hydrogen peroxide was used as the oxidizing agent, the target adamantanetriol was obtained with high selectivity and high yield, whereas Comparative Example 1 using sodium hypochlorite as the oxidizing agent was used. And 2, almost no adamantane triol can be obtained. Further, according to the results of Example 3 and Example 5, it was found that adamantane triol can be obtained with high selectivity and high yield in the case where the catalyst, the organic acid, and the oxidizing agent are added in portions, and the total amount of the primary addition.

又，參照特定之實施態樣對本發明進行了詳細說明，但同業者明白可於不脫離本發明之精神與範圍之情況下進行各種變更及修正。 The present invention has been described with reference to the specific embodiments thereof, and it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

本申請案係基於2012年6月6日提出申請之日本專利申請2012-128899者，將其內容作為參照而編入於此。 The present application is based on Japanese Patent Application No. 2012-128899, filed on Jun.

[產業上之可利用性] [Industrial availability]

根據本發明，可藉由以金剛烷類作為起始原料、廉價且環境負荷較少之方法而以高選擇性且高產率製造金剛烷三醇類。藉由本發明所得之金剛烷三醇類作為高功能性聚合物或電子材料、合成潤滑油、或醫農藥等之中間物而較為有用。 According to the present invention, adamantane triols can be produced with high selectivity and high yield by a method in which adamantane is used as a starting material, inexpensive and environmentally less loaded. The adamantane triol obtained by the present invention is useful as an intermediate between a highly functional polymer or an electronic material, a synthetic lubricating oil, or a medical pesticide.

Claims (14)

一種金剛烷三醇類之製造方法，其係使下述通式(1)所表示之金剛烷類於溶劑中且於金屬錯合物之存在下與過氧化氫反應， (式中，R表示鹵素原子、羥基、可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷基、可具有取代基之碳原子數3~10之烷基、可具有取代基之直鏈狀或支鏈狀之碳原子數1~10之烷氧基、可具有取代基之碳原子數3~10之環烷氧基、可具有取代基之碳原子數2~10之醯基、可具有取代基之碳原子數2~10之醯氧基、經取代或未經取代之芳基、經取代或未經取代之芳氧基；n表示0~13之整數，於n為2以上之情形時，複數個R相互可相同亦可不同；但，羥基之數量為兩個以下)。 A method for producing an adamantane triol, which comprises reacting an adamantane represented by the following formula (1) with a hydrogen peroxide in a solvent in the presence of a metal complex; (wherein R represents a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkyl group having 3 to 10 carbon atoms which may have a substituent; a linear or branched alkoxy group having 1 to 10 carbon atoms having a substituent, a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, and 2 to 10 carbon atoms which may have a substituent a mercapto group of 10, an alkenyloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group; n represents an integer of 0 to 13, When n is 2 or more, the plurality of Rs may be the same or different from each other; however, the number of hydroxyl groups is two or less). 如請求項1之金剛烷三醇類之製造方法，其係使上述通式(1)所表示之金剛烷類於溶劑中且於金屬錯合物及有機酸之存在下與過氧化氫反應。 The method for producing an adamantane triol according to claim 1, wherein the adamantane represented by the above formula (1) is reacted with hydrogen peroxide in a solvent in the presence of a metal complex and an organic acid. 如請求項1之金剛烷三醇類之製造方法，其中上述金剛烷三醇類為1,3,5-金剛烷三醇衍生物。 The method for producing an adamantane triol according to claim 1, wherein the adamantane triol is a 1,3,5-adamantane triol derivative. 如請求項1之金剛烷三醇類之製造方法，其中上述溶劑為水/有機溶劑之混合溶液。 The method for producing an adamantane triol according to claim 1, wherein the solvent is a mixed solution of water/organic solvent. 如請求項4之金剛烷三醇類之製造方法，其中上述有機溶劑為選自水溶性之醇類或腈類中之一種或兩種以上之有機溶劑。 The method for producing an adamantane triol according to claim 4, wherein the organic solvent is one or two or more organic solvents selected from the group consisting of water-soluble alcohols and nitriles. 如請求項4之金剛烷三醇類之製造方法，其中上述有機溶劑為乙腈。 The method for producing an adamantane triol according to claim 4, wherein the organic solvent is acetonitrile. 如請求項1之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，配位子之至少一個具有4~8個氮原子，其中複數個氮原子經由連續之2個碳原子而連結。 The method for producing an adamantane triol according to claim 1, wherein in the above metal complex, at least one of the ligands has 4 to 8 nitrogen atoms, wherein the plurality of nitrogen atoms are via two consecutive carbon atoms. link. 如請求項7之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，配位子之至少一個為下述通式(2)或(3)所表示之含氮化合物， (式中，R1~R4可相同亦可不同，表示氫原子或可具有取代基之碳原子數1~10之直鏈狀或支鏈狀之烷基；Ar1及Ar2可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基) (式中，Ar3~Ar5可相同亦可不同，表示經取代或未經取代之含氮芳香族雜環基)。 The method for producing an adamantane triol according to claim 7, wherein in the metal complex, at least one of the ligands is a nitrogen-containing compound represented by the following formula (2) or (3), (wherein R 1 to R 4 may be the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent; Ar 1 and Ar 2 may be the same Different, representing a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group) (In the formula, Ar 3 to Ar 5 may be the same or different and each represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group). 如請求項8之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，通式(2)中之R1~R4之鄰接之對中的至少一對以經由單鍵形成環之方式連結。 The method for producing an adamantane triol according to claim 8, wherein in the metal complex, at least one pair of adjacent pairs of R 1 to R 4 in the formula (2) forms a ring via a single bond The way to connect. 如請求項9之金剛烷三醇類之製造方法，其中於上述金屬錯合物中，通式(2)中之R1~R4之鄰接之對中的R1與R2、及R3與R4分別以經由單鍵形成環之方式連結。 The method for producing an adamantane triol according to claim 9, wherein in the metal complex, R 1 and R 2 and R 3 in the adjacent pair of R 1 to R 4 in the formula (2) Each of R 4 is linked to form a ring via a single bond. 如請求項第1至10項中任一項之金剛烷三醇類之製造方法，其中上述金屬錯合物之中心金屬為選自過渡金屬之金屬。 The method for producing an adamantane triol according to any one of claims 1 to 10, wherein the central metal of the metal complex is a metal selected from the group consisting of transition metals. 如請求項11之金剛烷三醇類之製造方法，其中上述金屬錯合物之中心金屬為鐵。 The method for producing an adamantane triol according to claim 11, wherein the central metal of the metal complex is iron. 如請求項2之金剛烷三醇類之製造方法，其中上述有機酸為脂肪族羧酸或芳香族羧酸。 The method for producing an adamantane triol according to claim 2, wherein the organic acid is an aliphatic carboxylic acid or an aromatic carboxylic acid. 如請求項13之金剛烷三醇類之製造方法，其中上述有機酸為乙酸。 The method for producing an adamantane triol according to claim 13, wherein the organic acid is acetic acid.
TW102120191A 2012-06-06 2013-06-06 Method for producing adamantanetriol TW201402529A (en)

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