JP6011867B2 - Dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex - Google Patents

Description

  The present invention relates to a novel dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex, a catalyst for multiple bond addition reaction comprising this gold complex, a catalyst for producing 2-oxazolidinone comprising this gold complex, and an aqueous solvent comprising this gold complex. The present invention relates to a catalyst for producing 2-oxazolidinone, a method for producing the gold complex, and a method for producing 2-oxazolidinone using the catalyst.

  A dendrimer has a molecular structure that branches like a tree from the central core, and consists of a central part called the core, a branched repeating part called the dendron, and a terminal group, which can control the molecular structure and molecular size highly. It is a possible polymer compound. Focusing on this unique structure, attempts have been made in recent years to use it as a functional polymer by introducing functional groups at various sites of the dendrimer (see Patent Document 1 and Non-Patent Document 1).

  One of them is to provide a dendrimer with a catalytic function. Many dendrimer-immobilized catalysts have been developed so far, most of which have the catalyst immobilized on the outermost layer of the dendrimer molecule and the catalyst immobilized on the core. (See Non-Patent Documents 2 and 3).

  For example, as a typical dendrimer-immobilized organometallic catalyst, a dendrimer-immobilized nickel complex catalyst having a diamine introduced at the end of the dendrimer as a bidentate ligand (see Non-Patent Document 4), a phosphine skeleton introduced into the core of the dendrimer And a dendrimer-immobilized palladium catalyst (see Non-Patent Document 5).

  In addition, the dendrimer-immobilized organometallic catalyst is nano-sized, so it is possible to easily recycle the catalyst by membrane separation using a separation membrane having nanopores, or by filtration and collection by reprecipitation due to high molecular weight. (See Non-Patent Documents 6 and 7). Further, when the catalytically active species is immobilized at the core portion, the solubility in the solvent can be adjusted by variously changing the functional group of the outermost layer, thereby improving the catalytic activity. Since the dendrimer has such an interesting feature, development of a novel dendrimer core part immobilization catalyst is demanded.

  In recent years, the effectiveness as a nitrogen-containing heterocyclic carbene ligand has been clarified, and the effectiveness of various carbene-transition metal complex catalysts has been reported. Dendrimer core part-immobilized carbene-rhodium complexes, dendrimer core part-immobilized carbene-palladium complexes, and the like prepared from these complexes in the dendrimer core part have recently been synthesized and their specific catalytic activity has been reported (Non-patent Document 8). 9). On the other hand, although a nitrogen-containing heterocyclic carbene-gold complex having a relatively small molecular weight has been reported recently (see Non-Patent Document 10), addition of small molecules such as carbon dioxide to multiple bonds is relatively large. A dendrimer having a nitrogen-containing heterocyclic carbene-gold complex effective in the reaction at the core has not been reported so far.

Japanese Patent No. 4822410

“Dendritic Polymers”, 2005, p.75 (NTS) "Dendrimer Catalysis", 2006, p. 1 (Springer) “Chemical Industry”, 2001, Vol. 52, p.933 “Nature”, 1994, Volume 372, p.659. “Tetrahedron Lett.”, 2007, Vol. 48, p. 6817 “Journal of American Chemical Society (J. Am. Chem. Soc.)”, 1996, Vol. 118, p. "Chem. Comm.", 2000, p.789 “Chemical Communication”, 2005, p. 4526 “Dalton Trans.”, 2008, p. 379 “Journal of Inorganic Biochemistry (J. Inorg. Biochem.)”, 2012, 106, p.52.

The present invention has been made under such circumstances, and provides a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex having high catalytic activity for addition reaction to multiple bonds, and a method for producing the same. This is the first purpose.
The second object of the present invention is to provide a catalyst for a multiple bond addition reaction such as a 2-oxazolidinone production reaction.
A third object of the present invention is to provide a method for producing 2-oxazolidinone using the catalyst.

The inventors of the present invention attempted to obtain a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex using gold instead of rhodium or palladium as the metal of the complex by the same production method as in Non-Patent Documents 8 and 9. did. However, a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex could not be obtained by the same production method as described in Non-Patent Documents 8 and 9.
The present inventors have analyzed each step in the production method and conducted extensive research. As a result, the production method is not effective when the metal of the complex is gold, and a dendrimer using a halogen-based reaction solvent. The reaction between the immobilized nitrogen-containing heterocyclic carbene and the gold (I) compound produces the target compound, a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex. When a halogen-based solvent described in References 8 and 9 and used in the reaction step is used as an eluent for column chromatography, the target compound is decomposed and the yield is greatly reduced. Since it is impossible to isolate, the dendrimer of the target compound is spherical and has a large molecular weight and does not crystallize. Purification by recrystallization is impossible, and the target compound can be isolated by using mainly ester solvents among the various solvents as the eluent during purification by column chromatography. Finally, the target compound is purified by column chromatography in a solvent by reacting a dendrimer-immobilized nitrogen-containing heterocyclic carbene prepared from a dendrimer-immobilized imidazolium salt with a gold (I) compound. In this case, it has been found that it can be easily obtained mainly by using an ester solvent as an eluent.
In addition, in the further research on the obtained dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex, this dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex efficiently promotes the reaction between propargylamine and carbon dioxide. It was found that the catalyst is useful as a catalyst for producing a new multiple bond, a catalyst for producing 2-oxazolidinone, and a catalyst for producing 2-oxazolidinone used in an aqueous solvent.
The present invention has been completed based on various findings obtained in the above-described research process.

［式中、Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス（トリフルオロメタンスルホニル）炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄（III）酸イオン、テトラブロモ鉄（III）酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス（トリフルオロメタンスルホニル）イミデートイオンである。Ｇは一般式（II）

（式中、Ｒ¹は炭素数１〜３のアルキル基、炭素数7のアラルキル基、又は(CH₂CH₂O)_mCH₃で表されるｍの平均=１〜２０のアルコキシ基である。ｎは１以上４以下の整数を示す。ｄ，ｅ及びｆのうち、少なくとも２つが１で、他は０である。但し、ｎが１で、かつ、Ｒ¹がアルキル基であるものは除外する）
で表される基である］
で表されるデンドリマー固定化含窒素複素環カルベン−金錯体。
（２）前記（１）記載のデンドリマー固定化含窒素複素環カルベン−金錯体から成る多重結合付加反応用触媒。
（３）前記（１）記載のデンドリマー固定化含窒素複素環カルベン−金錯体から成る２−オキサゾリジノン製造用触媒。
（４）前記（１）記載のデンドリマー固定化含窒素複素環カルベン−金錯体から成る水溶媒中で使用する２−オキサゾリジノン製造用触媒。
（５） 一般式（III）

［式中、Ｘはハロゲン原子、Ｇは一般式（II）

（式中、Ｒ¹は炭素数１〜３のアルキル基、炭素数7のアラルキル基、又は(CH₂CH₂O)_mCH₃で表されるｍの平均=１〜２０のアルコキシ基である。ｎは１以上４以下の整数を示す。ｄ，ｅ及びｆのうち、少なくとも２つが１で、他は０である。但し、ｎが１で、かつ、Ｒ¹がアルキル基であるものは除外する）
で表される基である］
で表されるデンドリマー固定化イミダゾリウム塩と酸化銀（Ｉ）とを溶媒中で反応させて、溶液中に含窒素複素環カルベンを生成する含窒素複素環カルベン生成工程、
デンドリマー固定化含窒素複素環カルベンが生成した溶液と、
ＡｕＬ[Ｓ(ＣＨ₃)₂] （ＩＶ）
（式中、Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス（トリフルオロメタンスルホニル）炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄（III）酸イオン、テトラブロモ鉄（III）酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス（トリフルオロメタンスルホニル）イミデートイオンを示す）
の組成で表される金（Ｉ）化合物とを混合し溶媒中で反応させる反応工程、及び、
前記反応工程で得られた生成物をエステル系溶媒を主要成分とする溶離液を用いたカラムクロマトグラフィーにより分離精製することを含む精製工程、
を備えることを特徴とする、一般式（Ｉ）

（式中、Ｇ及びＬは、前記と同じ意味を示す）
で表されるデンドリマー固定化含窒素複素環カルベン−金錯体の製造方法。
（６）前記（２）〜（４）のいずれか１項に記載の触媒と二酸化炭素の存在下、一般式（VIII）

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、水素原子又は炭化水素基であって、これらのうち２つ以上が炭化水素基の場合、いずれか２つは互いに結合して環を形成してもよい）
で表されるプロパルギルアミンを溶媒中で反応させ、一般式（IX）

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、前記と同じ意味を示す）
で表される２−オキサゾリジノンを製造することを特徴とする、２−オキサゾリジノン製造方法。 That is, this application provides the following inventions.
(1) General formula (I)

[Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Trifluoromethanesulfonyl) imidate ion. G is the general formula (II)

(In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0. Here, n is 1, and those wherein R ¹ is alkyl group exclude)
Is a group represented by
And a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex.
(2) A catalyst for multiple bond addition reaction comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (1).
(3) A catalyst for producing 2-oxazolidinone comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (1).
(4) A catalyst for producing 2-oxazolidinone used in an aqueous solvent comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex described in (1).
(5) General formula (III)

[Wherein X is a halogen atom, G is a general formula (II)

(In the formula, R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0. Here, n is 1, and those wherein R ¹ is alkyl group exclude)
Is a group represented by
A nitrogen-containing heterocyclic carbene producing step for producing a nitrogen-containing heterocyclic carbene in a solution by reacting a dendrimer-immobilized imidazolium salt represented by formula (I) with silver (I) oxide in a solvent;
A solution in which a dendrimer-immobilized nitrogen-containing heterocyclic carbene is formed;
AuL [S (CH ₃ ) ₂ ] (IV)
(Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Indicates (trifluoromethanesulfonyl) imidate ion)
A reaction step of mixing a gold (I) compound represented by the following composition and reacting in a solvent; and
A purification step comprising separating and purifying the product obtained in the reaction step by column chromatography using an eluent containing an ester solvent as a main component;
Comprising the general formula (I)

(In the formula, G and L have the same meaning as described above.)
The manufacturing method of the dendrimer fixed nitrogen-containing heterocyclic carbene-gold complex represented by these.
(6) In the presence of the catalyst according to any one of (2) to (4) and carbon dioxide, the general formula (VIII)

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or hydrocarbon groups, and when two or more of them are hydrocarbon groups, any two are bonded to each other to form a ring. May be formed)
Is reacted with propargylamine represented by the general formula (IX)

(Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above)
The 2-oxazolidinone represented by these is manufactured, The 2-oxazolidinone manufacturing method characterized by the above-mentioned.

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、水素原子又は炭化水素基であって、これらのうち２つ以上が炭化水素基の場合、いずれか２つは互いに結合して環を形成してもよい）
で表されるプロパルギルアミンを溶媒中で反応させ、一般式（IX）

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、前記と同じ意味を示す）
で表される２−オキサゾリジノンを製造することを特徴とする、２−オキサゾリジノン製造方法。
（２１）溶媒が水であることを特徴とする、前記（６）又は（２０）に記載の２−オキサゾリジノン製造方法。 Furthermore, the present invention can include the following aspects.
(7) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (1) above, wherein R ¹ is an alkoxy group having an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1-20. .
(8) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (1) or (7), wherein the average m is 3 to 12.
(9) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (1), wherein n is an integer of 2 or more and 4 or less, and R ¹ is an alkyl group having 1 to 3 carbon atoms.
(10) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (1) and (7) to (9), wherein d, e and f are 1.
(11) The dendrimer-immobilized nitrogen-containing heterocyclic carbene according to any one of (1) and (7) to (9), wherein two of d, e and f are 1 and 1 is 0 A gold complex.
(12) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (1) and (7) to (11), wherein L is a halide ion.
(13) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (1) and (7) to (12), wherein two Gs in the general formula (I) are the same.
(14) The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (1) and (7) to (13), wherein the plurality of R ¹ in the general formula (II) are all the same. .
(15) A catalyst for multiple bond addition reaction comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (7) to (14).
(16) A catalyst for producing 2-oxazolidinone comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (7) to (14).
(17) A catalyst for producing 2-oxazolidinone used in an aqueous solvent comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to any one of (7) to (14).
(18) The method for producing a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (5), wherein the purification step includes filtration using a solvent containing an ester solvent as a main component.
(19) The method for producing a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to (5) or (18), wherein the ester solvent is ethyl acetate.
(20) In the presence of the catalyst according to any one of (14) to (17) and carbon dioxide, a general formula

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or hydrocarbon groups, and when two or more of them are hydrocarbon groups, any two are bonded to each other to form a ring. May be formed)
Is reacted with propargylamine represented by the general formula (IX)

(Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above)
The 2-oxazolidinone represented by these is manufactured, The 2-oxazolidinone manufacturing method characterized by the above-mentioned.
(21) The method for producing 2-oxazolidinone according to (6) or (20), wherein the solvent is water.

  The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex represented by the general formula (I) according to the present invention is useful as a catalyst for multiple bond addition reaction. For example, when this is used, it is used in a non-aqueous solvent. The reaction of propargylamine and carbon dioxide proceeds not only in water but also in water at a relatively low temperature such as room temperature, and 2-oxazolidinone can be obtained with good yield.

［式中、Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス（トリフルオロメタンスルホニル）炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄（III）酸イオン、テトラブロモ鉄（III）酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス（トリフルオロメタンスルホニル）イミデートイオンである。Ｇは一般式（II）

（式中、Ｒ¹は炭素数１〜３のアルキル基、炭素数７のアラルキル基、又は(CH₂CH₂O)_mCH₃で表されるｍの平均=１〜２０のアルコキシ基である。ｎは１以上４以下の整数を示す。ｄ，ｅ及びｆのうち、少なくとも２つが１で、他は０である。但し、ｎが１で、かつ、Ｒ¹がアルキル基であるものは除外する）
で表される基である］
で表される。 The novel dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex of the present invention has the following general formula (I)

[Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Trifluoromethanesulfonyl) imidate ion. G is the general formula (II)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0. Here, n is 1, and those wherein R ¹ is alkyl group exclude)
Is a group represented by
It is represented by

  About these dendrimers, the structure shown by each code | symbol in the substituent in the said formula is demonstrated concretely, and those structures are further clarified. First, the general formula (I) will be described.

(1) R ¹ represents an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. The alkyl group having 1 to 3 carbon atoms is a group selected from methyl, ethyl, n-propyl and i-propyl.
A C7 aralkyl group represents a benzyl group.
The average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 represents that the average of m is 1 to 20, and one molecule and / or a plurality of molecules There may be a single unit, but it is not necessarily required to be a single unit. Therefore, the value of the general formula 3 shown by (II) R ¹ each m may not be the same.
(2) The generation number n of the repeating structure is an integer of 1 or more and 4 or less.
(3) At least two of d, e, and f are 1 and the others are 0.
As an example of the group represented by the symbol G, any two of d, e, and f are 1 and n = 3 is as follows.
_{-CH 2 -C 6 H 3 - [} O-CH 2 -C 6 H 3 - [O-CH 2 -C 6 H 3 - (O-R 1) 2] 2] 2
(4) Excludes those in which R ¹ is an alkyl group and n is 1, which has a relatively low molecular weight and can be purified by recrystallization.

（式中、ｄ，ｅ及びｆは、前記と同じ意味を示す） In the dendrimer of the general formula (I), the repeating structure is represented by the general formula (V).

(Wherein d, e and f have the same meaning as described above)

[式中、Ｘはハロゲン原子、Ｇは一般式（II）

（式中、Ｒ¹は炭素数１〜３のアルキル基、炭素数７のアラルキル基、又は(CH₂CH₂O)_mCH₃で表されるｍの平均=１〜２０のアルコキシ基である。ｎは１以上４以下の整数を示す。
ｄ，ｅ及びｆのうち、少なくとも２つが１で、他は０である。但し、ｎが１で、かつ、Ｒ¹がアルキル基であるものは除外する）
で表される基である］
で表されるデンドリマー固定化イミダゾリウム塩と酸化銀（Ｉ）とを溶媒中で反応させることにより得られる含窒素複素環カルベンの溶液と、
ＡｕＬ[Ｓ(ＣＨ₃)₂] （ＩＶ）
（式中、Ｌはハロゲン化物イオン、トリフルオロメタンスルホン酸イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、ヘキサフルオロアンチモネートイオン、トリス（トリフルオロメタンスルホニル）炭素酸イオン、トリフルオロ酢酸イオン、有機カルボン酸イオン、硝酸イオン、硫酸水素イオン、テトラクロロ鉄（III）酸イオン、テトラブロモ鉄（III）酸イオン、トルエンスルホン酸イオン、チオシアン酸イオン、シアン化物イオン、アジ化物イオン、又はビス（トリフルオロメタンスルホニル）イミデートイオンを示す）
の組成で表される金（Ｉ）化合物とを混合し溶媒中で反応させ、反応生成物を所定の手段により精製することにより製造することができる。 The production of the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex (I) of the present invention will be described.
General formula (III)

[Wherein X is a halogen atom, G is a general formula (II)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. N represents an integer of 1 or more and 4 or less.
At least two of d, e, and f are 1 and the others are 0. (However, the case where n is 1 and R ¹ is an alkyl group is excluded)
Is a group represented by
A solution of a nitrogen-containing heterocyclic carbene obtained by reacting a dendrimer-immobilized imidazolium salt represented by formula (I) with silver (I) in a solvent;
AuL [S (CH ₃ ) ₂ ] (IV)
(Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Indicates (trifluoromethanesulfonyl) imidate ion)
And a gold (I) compound represented by the following composition is mixed and reacted in a solvent, and the reaction product is purified by a predetermined means.

First, the corresponding nitrogen-containing heterocyclic carbene is obtained by reaction with silver (I) oxide.
As the reaction solvent, a solvent that can dissolve the dendrimer-immobilized imidazolium salt moderately and does not participate in the reaction is used. Specifically, 1,2-dichloroethane, N, N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran, diethyl ether and the like are preferable, and these solvents are used alone or in the form of a mixed solvent. Among these, a preferred reaction solvent is 1,2-dichloroethane.

The amount of silver (I) oxide to be used is not necessarily limited, but is generally 0.5 to 4 mol, preferably 0.5 to 2 per mol of dendrimer-immobilized imidazolium salt. A molar range of silver (I) oxide is used.
When the reaction between the dendrimer-immobilized imidazolium salt and silver (I) oxide is performed using this solvent, the dendrimer-immobilized imidazolium salt is preferably added to the solvent in an inert gas atmosphere such as argon. After adding a necessary amount of silver (I) to the resulting solution, the reaction is conducted with sufficient stirring.

Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 160 ° C., but the upper limit differs depending on the boiling point of each solvent. The reaction time varies depending on other conditions such as the reaction temperature and the solvent used, and cannot be determined unconditionally, but is preferably about 2 to 50 hours.
A part of the reaction solution was taken out, and the ¹ H-NMR measurement confirmed that the dendrimer-immobilized imidazolium salt disappeared and a dendrimer-immobilized carbene was produced.

  After confirming the formation of the dendrimer-immobilized carbene, by adding a gold (I) compound to this solution, dimethyl sulfide is dissociated and a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex is generated.

The amount of the gold (I) compound to be used is not necessarily limited, but generally 1 to 4 mol, preferably 1 to 1.5 mol, per mol of the dendrimer-immobilized nitrogen-containing heterocyclic carbene. A range of gold (I) compounds is used.
When the reaction between the dendrimer-immobilized nitrogen-containing heterocyclic carbene and the gold (I) compound is performed, preferably, a necessary amount of gold (in the dendrimer-immobilized nitrogen-containing heterocyclic carbene solution is added in an inert gas atmosphere such as argon. I) After adding a compound, it is made to react, fully stirring.

Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 80 ° C., but proceeds sufficiently at about room temperature. The reaction time varies depending on other conditions such as the reaction temperature and the solvent used, and cannot be determined unconditionally, but is preferably about 1 to 20 hours.
A part of the reaction solution was taken out, and from this ¹ H-NMR measurement, it was confirmed that a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex was produced.

After completion of the reaction, the solvent, silver compound, excess gold (I) compound and the like are separated and removed by distillation under reduced pressure and filtration, and the desired product is obtained by column chromatography, which is confirmed by ¹ H-NMR measurement.
As an eluent for column chromatography, an eluent containing an ester solvent such as ethyl acetate, methyl acetate, ethyl propionate, or methyl propionate as a main component is used. A mixed solvent of an ester solvent and a hydrocarbon solvent such as hexane or toluene, or an alcohol solvent such as methanol or ethanol may be used.
When a halogen-based solvent is used as an eluent for column chromatography, the target product is decomposed, and the yield is greatly reduced. Moreover, the product which is originally white turns gray and a pure product cannot be obtained. Examples of the halogen solvent include dichloromethane, 1,2-dichloroethane, chloroform and the like. In the production of the dendrimer-immobilized nitrogen-containing heterocyclic carbene-rhodium complex described in Non-Patent Document 9, dichloromethane is used in the purification step by filtration or column chromatography. -In the production of the gold complex, it is most preferable not to use a halogen-based solvent such as dichloromethane in the purification step, but even if it is used, the amount used is 10 vol.% Or less, preferably 5 vol.% Of the solvent for purification. Hereinafter, it is necessary to limit to 2 vol.% Or less.
The ratio of the ester solvent in the purification solvent such as eluent used for filtration or column chromatography is usually 50 to 100 vol.%, Preferably 60 to 100 vol.%, More preferably 80 to 100 vol.%, Most preferably, it is 90-100 vol.%.
Nitrogen-containing heterocyclic carbene gold-complex generally including commercially available chloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold (I) is purified by recrystallization. Since it is spherical and has a large molecular weight and does not crystallize, it cannot be purified by recrystallization and is purified by column chromatography as described above.

  By these reactions, the target dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex can be produced in one pot.

で表されるイミダゾールと、一般式（VII）

（式中、Ｒ¹は炭素数１〜３のアルキル基、炭素数７のアラルキル基、又は(CH₂CH₂O)_mCH₃で表されるｍの平均=１〜２０のアルコキシ基である。ｎは１以上４以下の整数を示す。ｄ，ｅ及びｆのうち、少なくとも２つが１で、他は０である。Ｘはハロゲン原子（フッ素、塩素、臭素及びヨウ素）を示す。ｎは１以上４以下の整数を示す。但し、ｎが１で、かつ、Ｒ¹がアルキル基であるものは除外する）
で表されるハロ置換デンドロンを、必要に応じ塩基を存在させ溶媒中で反応させることにより製造することができる。
The dendrimer-immobilized imidazolium salt used as a raw material has the formula (VI)

An imidazole represented by the general formula (VII)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0 .X is .n which a halogen atom (fluorine, chlorine, bromine and iodine) An integer of 1 or more and 4 or less, except that n is 1 and R ¹ is an alkyl group.
Can be produced by reacting in a solvent in the presence of a base, if necessary.

  In these production methods, the nitrogen atom of imidazole nucleophilic attacks on the carbon atom adjacent to the halogen atom, so N-benzylation (introduction of dendron) proceeds sequentially, and finally a dendrimer-immobilized imidazolium salt is produced. The

Examples of the base to be used include cesium fluoride, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like, among which cesium fluoride is preferable. These bases may be immobilized on an inorganic carrier such as celite.
The amount of base used is not necessarily limited, but in general, a base in the range of 1 to 3 moles, preferably 1 to 1.5 moles, is used per mole of hydrogen halide produced. It is done.

As the reaction solvent, a solvent that can dissolve imidazole and halo-substituted dendron moderately and does not participate in the reaction is used. Specifically, halogenated hydrocarbons such as N, N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran, diethyl ether, and dichloromethane are preferable, and these solvents are used alone or in the form of a mixed solvent. Among them, preferred reaction solvents include N, N-dimethylformamide, acetonitrile, and mixed solvents thereof.
When the reaction between imidazole and halo-substituted dendron is carried out using this solvent, it is preferable to add a necessary amount of base to the solution obtained by adding imidazole and halo-substituted dendron to the solvent in an inert gas atmosphere such as argon. Is added, and the mixture is allowed to react with sufficient stirring.

Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 160 ° C., but the upper limit differs depending on the boiling point of each solvent. The reaction time varies depending on other conditions such as the reaction temperature and the solvent used, and cannot be determined unconditionally, but is preferably about 2 to 50 hours.
The amount of the halo-substituted dendron is not necessarily limited, but in general, the halo-substituted dendron is in the range of 1 to 3 mol, preferably 1 to 1.3 mol, per mol of dendron introduced. Is used.

After completion of the reaction, the reaction product is obtained by separating and removing the solvent and unreacted substances, and the production of the target product is confirmed by ¹ H-NMR measurement.
By this reaction, the target dendrimer-immobilized imidazolium salt can be produced in one step.

  By using the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex, the reaction between propargylamine and carbon dioxide and the hydration reaction of the acetylene compound proceed. It is useful as a catalyst for multiple bond addition reaction.

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、水素原子又は炭化水素基であって、これらのうち２つ以上が炭化水素基の場合、いずれか２つは互いに結合して環を形成してもよい）
で表されるプロパルギルアミンを溶媒中で反応させ、一般式（IX）

（式中、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は、前記と同じ意味を示す）
で表される２−オキサゾリジノンを製造することができる。 An example of the reaction using the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex of the present invention as such a catalyst for multiple bond addition reaction will be described below.
In the presence of a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex and carbon dioxide as the catalyst, a compound of the general formula (VIII)

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or hydrocarbon groups, and when two or more of them are hydrocarbon groups, any two are bonded to each other to form a ring. May be formed)
Is reacted with propargylamine represented by the general formula (IX)

(Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above)
2-oxazolidinone represented by can be produced.

The hydrocarbon group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
This reaction is usually carried out by dissolving the catalyst and the raw material in a solvent under a carbon dioxide-containing atmosphere (preferably under a carbon dioxide atmosphere). As the solvent, an organic solvent or water is usually used. Protic solvents such as methanol, isopropanol, and t-butyl alcohol are preferably used as the organic solvent, but aprotic polar solvents such as acetonitrile and dioxane can also be used, and these are used alone or in combination. The pressure (or partial pressure) of carbon dioxide may be 0.1 MPa (1 atm), but may be increased to 10 MPa. Usually, it is performed in the range of 0.1 MPa to 2 MPa.

The reaction can be allowed to proceed at about room temperature without special heating, but may be accelerated by heating. During the reaction, the reaction solution is preferably stirred.

  After completion of the reaction, the reaction solution was distilled off under reduced pressure, and a concentrated solution such as toluene was dropped into alcohol such as methanol or diethyl ether and reprecipitated, whereby a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold catalyst was obtained. It can be recovered and recycled. Also, the target substance can be obtained by concentrating the supernatant liquid alcohol or diethyl ether and separating and purifying by column chromatography.

In particular, when the outermost layer R ¹ of the dendrimer is an alkoxy group represented by (CH ₂ CH ₂ O) _m CH ₃ , 2-oxazolidinone that is the target substance can be obtained in high yield in water at room temperature. When the outermost layer is a hydrophilic group as described above, the catalyst is recovered and can be recycled by reprecipitation by dropping the reaction solution into diethyl ether.

In this catalyst, by selecting the combination of the outermost layer R ¹ and the reaction solvent, the target substance 2-oxazolidinone can be obtained with good yield at room temperature, and the catalyst is recovered and recycled by reprecipitation. This is an advantage of this catalyst.

  Thus, the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex of the present invention is useful as a novel catalyst for multiple bond addition reaction, a catalyst for producing 2-oxazolidinone, and a catalyst for producing 2-oxazolidinone used in an aqueous solvent. For example, by using this, the reaction between propargylamine and carbon dioxide can be efficiently promoted in a solvent.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

で表されるデンドリマー固定化イミダゾリウム塩３５４.２ｍｇの１，２−ジクロロエタン溶液（５ｍｌ）に酸化銀（Ｉ）４３.０ｍｇを加え、６０℃にて１８時間攪拌した。
この１，２−ジクロロエタン溶液に、クロロ（ジメチルスルフィド）金（Ｉ）ＡｕＣｌ[Ｓ(ＣＨ₃)₂]１０６.８ｍｇを加え、室温で３時間撹拌し反応させた。
このようにして得られた反応液を減圧下で溶媒を留去し酢酸エチルでセライト濾過し、濾液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（酢酸エチル：メタノール＝１０：１）で精製した（無色油状、収量２８９.２ｍｇ、収率７０.７％）。
このものの核磁気共鳴スペクトル分析と元素分析の結果は次の通りである。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ₃）δ／ｐｐｍ ６.８６（ｓ，２Ｈ），６.４９（ｄ，４Ｈ，Ｊ＝２.２Ｈｚ），６.４５（ｔ，２Ｈ，Ｊ＝２.１Ｈｚ），５.２６（ｓ，４Ｈ），４.０９（ｔ，８Ｈ，Ｊ＝４.７Ｈｚ），３.８３（ｔ，８Ｈ，Ｊ＝４.７Ｈｚ），３.７５−３.６３（ｍ，２４Ｈ），３.５７−３.５３（ｍ，８Ｈ），３.３８（ｓ，１２Ｈ）
元素分析：Ｃ ４７.６５％、Ｈ ６.４３％、Ｎ ２.３１％、Ｃｌ ２.８１％（測定値）。Ｃ ４７.８５％、Ｈ ６.４３％、Ｎ ２.４８％、Ｃｌ ３.１４％（計算値）。
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

Example 1
Under the argon atmosphere, the following structural formula

Into a 1,2-dichloroethane solution (5 ml) of 354.2 mg of the dendrimer-immobilized imidazolium salt represented by the formula, 43.0 mg of silver (I) was added and stirred at 60 ° C. for 18 hours.
To this 1,2-dichloroethane solution, 106.8 mg of chloro (dimethylsulfide) gold (I) AuCl [S (CH ₃ ) ₂ ] was added and stirred at room temperature for 3 hours for reaction.
The reaction solution thus obtained was evaporated under reduced pressure, filtered through Celite with ethyl acetate, the filtrate was evaporated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (ethyl acetate: (Methanol = 10: 1) for purification (colorless oil, yield 289.2 mg, yield 70.7%).
The results of nuclear magnetic resonance spectrum analysis and elemental analysis of this product are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 6.86 (s, 2H), 6.49 (d, 4H, J = 2.2 Hz), 6.45 (t, 2H, J = 2.1 Hz) ), 5.26 (s, 4H), 4.09 (t, 8H, J = 4.7 Hz), 3.83 (t, 8H, J = 4.7 Hz), 3.75-3.63 (m , 24H), 3.57-3.53 (m, 8H), 3.38 (s, 12H)
Elemental analysis: C 47.65%, H 6.43%, N 2.31%, Cl 2.81% (measured value). C 47.85%, H 6.43%, N 2.48%, Cl 3.14% (calculated).
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるデンドリマー固定化イミダゾリウム塩６７１.８ｍｇの１，２−ジクロロエタン溶液（５ｍｌ）に酸化銀（Ｉ）１５１.８ｍｇを加え、７０℃にて２７時間攪拌した。
この１，２−ジクロロエタン溶液に、クロロ（ジメチルスルフィド）金（Ｉ）ＡｕＣｌ[Ｓ(ＣＨ₃)₂]１４９.０ｍｇを加え、室温で３時間撹拌し反応させた。
このようにして得られた反応液を減圧下で溶媒を留去し酢酸エチルでセライト濾過し、濾液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（酢酸エチル：メタノール＝３：１）で精製した（無色油状、収量６６９.３ｍｇ、収率８９.５％）。
このものの核磁気共鳴スペクトル分析と元素分析の結果は次の通りである。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ／ｐｐｍ ６.８７（ｓ，２Ｈ），６.４９（ｄ，４Ｈ，Ｊ＝２.１Ｈｚ），６.４５（ｔ，２Ｈ，Ｊ＝２.１Ｈｚ），５.２６（ｓ，４Ｈ），４.０９（ｔ，８Ｈ，Ｊ＝４.７Ｈｚ），３.８３（ｔ，８Ｈ，Ｊ＝４.７Ｈｚ），３.７３−３.６２（ｍ，５６Ｈ），３.５６−３.５２（ｍ，８Ｈ），３.３７（ｓ，１２Ｈ）
元素分析：Ｃ ４９.５４％、Ｈ ７.０９％、Ｎ １.７７％、Ｃｌ ２.２１％（測定値）。Ｃ ４９.４４％、Ｈ ７.０７％、Ｎ １.８９％、Ｃｌ ２.３９％（計算値）。
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

(Example 2)
Under the argon atmosphere, the following structural formula

151.8 mg of silver (I) oxide was added to a 1,2-dichloroethane solution (5 ml) of 671.8 mg of the dendrimer-immobilized imidazolium salt represented by the following formula, and stirred at 70 ° C. for 27 hours.
To this 1,2-dichloroethane solution, 149.0 mg of chloro (dimethylsulfide) gold (I) AuCl [S (CH ₃ ) ₂ ] was added and stirred at room temperature for 3 hours to react.
The reaction solution thus obtained was evaporated under reduced pressure, filtered through Celite with ethyl acetate, the filtrate was evaporated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (ethyl acetate: (Methanol = 3: 1) for purification (colorless oil, yield 669.3 mg, yield 89.5%).
The results of nuclear magnetic resonance spectrum analysis and elemental analysis of this product are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 6.87 (s, 2H), 6.49 (d, 4H, J = 2.1 Hz), 6.45 (t, 2H, J = 2.1 Hz) ), 5.26 (s, 4H), 4.09 (t, 8H, J = 4.7 Hz), 3.83 (t, 8H, J = 4.7 Hz), 3.73-3.62 (m , 56H), 3.56-3.52 (m, 8H), 3.37 (s, 12H)
Elemental analysis: C 49.54%, H 7.09%, N 1.77%, Cl 2.21% (measured value). C 49.44%, H 7.07%, N 1.89%, Cl 2.39% (calculated).
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるデンドリマー固定化イミダゾリウム塩１２６.５ｍｇの１，２−ジクロロエタン溶液（１ｍｌ）に酸化銀（Ｉ）１６.５ｍｇを加え、７５℃にて４８時間攪拌した。
この１，２−ジクロロエタン溶液に、クロロ（ジメチルスルフィド）金（Ｉ）ＡｕＣｌ[Ｓ(ＣＨ_３)_２]１０.０ｍｇを加え、室温で３時間撹拌し反応させた。
このようにして得られた反応液を減圧下で溶媒を留去し酢酸エチルでセライト濾過し、濾液を減圧下で溶媒留去し、得られた粗生成物をアルミナカラムクロマトグラフィー（酢酸エチル：メタノール＝１０：１）で精製した（無色油状、収量７６.５ｍｇ、収率５７.４％）。
このものの核磁気共鳴スペクトル分析と元素分析の結果は次の通りである。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤ₃ＣＮ）δ／ｐｐｍ ７.２４（ｓ，２Ｈ），６.７５（ｓ，４Ｈ），５.２１（ｓ，４Ｈ），４.１３−４.０２（ｍ，１２Ｈ），３.８０−３.３２（ｍ，２７６Ｈ），３.２９（ｓ，１８Ｈ）
元素分析：Ｃ ５２.６６％、Ｈ ８.４７％、Ｎ ０.６７％、Ｃｌ ０.９２％（測定値）。Ｃ ５２.３３％、Ｈ ８.３１％、Ｎ ０.７３％、Ｃｌ ０.９３％（計算値）。
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

(Example 3)
Under the argon atmosphere, the following structural formula

16.5 mg of silver (I) oxide was added to 126.5 mg of a 1,2-dichloroethane solution (1 ml) of the dendrimer-immobilized imidazolium salt represented by the formula below and stirred at 75 ° C. for 48 hours.
To this 1,2-dichloroethane solution, 10.0 mg of chloro (dimethylsulfide) gold (I) AuCl [S (CH ₃ ) ₂ ] was added and stirred at room temperature for 3 hours for reaction.
The reaction solution thus obtained was distilled off the solvent under reduced pressure and filtered through celite with ethyl acetate, the filtrate was evaporated under reduced pressure, and the resulting crude product was subjected to alumina column chromatography (ethyl acetate: (Methanol = 10: 1) for purification (colorless oil, yield 76.5 mg, yield 57.4%).
The results of nuclear magnetic resonance spectrum analysis and elemental analysis of this product are as follows.
¹ H-NMR (400 MHz, CD ₃ CN) δ / ppm 7.24 (s, 2H), 6.75 (s, 4H), 5.21 (s, 4H), 4.13-4.02 (m , 12H), 3.80-3.32 (m, 276H), 3.29 (s, 18H)
Elemental analysis: C 52.66%, H 8.47%, N 0.67%, Cl 0.92% (measured value). C 52.33%, H 8.31%, N 0.73%, Cl 0.93% (calculated).
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるデンドリマー固定化イミダゾリウム塩４４８.７ｍｇの１，２−ジクロロエタン溶液（３ｍｌ）に酸化銀（Ｉ）２４.５ｍｇを加え、７５℃にて４８時間攪拌した。
この１，２−ジクロロエタン溶液に、クロロ（ジメチルスルフィド）金（Ｉ）ＡｕＣｌ[Ｓ(ＣＨ_３)_２]６５.３ｍｇを加え、室温で3時間撹拌し反応させた。
このようにして得られた反応液を減圧下で溶媒を留去し酢酸エチルでセライト濾過し、濾液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（酢酸エチル：ヘキサン＝３：２）で精製した（白色固体、収量３３６.６ｍｇ、収率６９.９％）。
このものの核磁気共鳴スペクトル分析と元素分析の結果は次の通りである。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ₃）δ／ｐｐｍ ６.７５（ｓ，２Ｈ），６.６３（ｄ，８Ｈ，Ｊ＝２.０Ｈｚ），６.５６（ｄ，１６Ｈ，Ｊ＝２.４Ｈｚ），６.５４（ｔ，４Ｈ，Ｊ＝２.２Ｈｚ），６.５１（ｔ，２Ｈ，Ｊ＝２.０Ｈｚ），６.４５（ｔ，４Ｈ，Ｊ＝２.０Ｈｚ），６.３９（ｔ，８Ｈ，Ｊ＝２.２Ｈｚ），５.２０（ｓ，４Ｈ），４.９６（ｓ，１６Ｈ），４.９２（ｓ，８Ｈ），３.７６（ｓ，４８Ｈ）
元素分析：Ｃ ６２.８７％、Ｈ ５.４０％、Ｎ １.０８％、Ｃｌ １.４７％（測定値）。Ｃ ６２.８９％、Ｈ ５.４１％、Ｎ １.２５％、Ｃｌ １.５９％（計算値）。
これらの分析結果より、この生成物は以下の構造式で表される化合物と同定された。

Example 4
Under the argon atmosphere, the following structural formula

24.5 mg of silver (I) was added to 448.7 mg of 1,2-dichloroethane solution (3 ml) of the dendrimer-immobilized imidazolium salt represented by the formula below and stirred at 75 ° C. for 48 hours.
To this 1,2-dichloroethane solution, 65.3 mg of chloro (dimethylsulfide) gold (I) AuCl [S (CH ₃ ) ₂ ] was added and stirred at room temperature for 3 hours to react.
The reaction solution thus obtained was evaporated under reduced pressure, filtered through Celite with ethyl acetate, the filtrate was evaporated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (ethyl acetate: (Hexane = 3: 2) (white solid, yield 336.6 mg, yield 69.9%).
The results of nuclear magnetic resonance spectrum analysis and elemental analysis of this product are as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ / ppm 6.75 (s, 2H), 6.63 (d, 8H, J = 2.0 Hz), 6.56 (d, 16H, J = 2.4 Hz) ), 6.54 (t, 4H, J = 2.2 Hz), 6.51 (t, 2H, J = 2.0 Hz), 6.45 (t, 4H, J = 2.0 Hz), 6.39 (T, 8H, J = 2.2 Hz), 5.20 (s, 4H), 4.96 (s, 16H), 4.92 (s, 8H), 3.76 (s, 48H)
Elemental analysis: C 62.87%, H 5.40%, N 1.08%, Cl 1.47% (measured value). C 62.89%, H 5.41%, N 1.25%, Cl 1.59% (calculated).
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるデンドリマー固定化イミダゾリウム塩４５０.０ｍｇの１，２−ジクロロエタン溶液（４.５ｍｌ）に酸化銀（Ｉ）２５.３ｍｇを加え、７５℃にて４８時間攪拌した。
この１，２−ジクロロエタン溶液に、クロロ（ジメチルスルフィド）金（Ｉ）ＡｕＣｌ[Ｓ(ＣＨ_３)_２]６３.５ｍｇを加え、室温で３時間撹拌し反応させた。
このようにして得られた反応液を減圧下で溶媒を留去しジクロロメタンでセライト濾過し、濾液を減圧下で溶媒留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー（ジクロロメタン：酢酸エチル＝４０：１）で精製した（灰色固体、収量９２.０ｍｇ、目的物質である場合の収率１９.１％）。
このものの元素分析の結果は次の通りである。
元素分析：Ｃ ６３.４５％、Ｈ ５.４５％、Ｎ １.１８％、Ｃｌ １.７９％（測定値）。Ｃ ６２.８９％、Ｈ ５.４１％、Ｎ １.２５％、Ｃｌ １.５９％（計算値）。
これらの分析結果より、この生成物は以下の構造式で表される化合物を含むかもしれないが、化合物の色、及び元素分析の結果より、含んだとしても純品ではない。

(Comparative example)
Under the argon atmosphere, the following structural formula

25.3 mg of silver (I) oxide was added to a 1,2-dichloroethane solution (4.5 ml) of the dendrimer-immobilized imidazolium salt represented by the formula (4) and stirred at 75 ° C. for 48 hours.
To this 1,2-dichloroethane solution, 63.5 mg of chloro (dimethylsulfide) gold (I) AuCl [S (CH ₃ ) ₂ ] was added and stirred at room temperature for 3 hours to react.
The reaction solution thus obtained was distilled off the solvent under reduced pressure and filtered through celite with dichloromethane. The filtrate was evaporated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (dichloromethane: ethyl acetate). = 40: 1) (gray solid, yield 92.0 mg, yield 19.1% when desired substance).
The results of elemental analysis of this product are as follows.
Elemental analysis: C 63.45%, H 5.45%, N 1.18%, Cl 1.79% (measured value). C 62.89%, H 5.41%, N 1.25%, Cl 1.59% (calculated).
From these analysis results, this product may contain a compound represented by the following structural formula, but it is not a pure product even if it is included due to the color of the compound and the result of elemental analysis.

で表されるプロパルギルアミン１１４.４ｍｇを順次加えた後、１気圧の二酸化炭素雰囲気下にて、室温で２４時間撹拌した。反応後、メタノール、ジクロロメタンと内部標準として３−ヒドロキシベンジルアルコールを加え均一とした後、一部取り出し減圧下で溶媒留去し、^１Ｈ−ＮＭＲより以下の化学式

で表される２−オキサゾリジノンの生成を確認した（収率８０％） (Example 5)
Under argon atmosphere, water (0.8 mL), dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex 11.8 mg (1 mol% based on amine) obtained in Example 2, and the following structural formula

After sequentially adding 114.4 mg of propargylamine represented by the formula, the mixture was stirred at room temperature for 24 hours under a carbon dioxide atmosphere of 1 atm. After the reaction, methanol, dichloromethane and 3-hydroxybenzyl alcohol as an internal standard were added and homogenized, and then a part was taken out and the solvent was distilled off under reduced pressure. From ¹ H-NMR, the following chemical formula

The production | generation of 2-oxazolidinone represented by this was confirmed (yield 80%).

(Example 6)
Gn [R] in the following Tables 1 and 2 produced in the same manner as in Example 1-4 (wherein n represents the same meaning as n in the general formula (II). D and f in the general formula (II) are 1 and e are 0. [TEG] means that R ¹ is an alkoxy group of m = 3, and [PEG] means that R ¹ is an alkoxy group of m = 5) 2-oxazolidinone was synthesized in the same manner as in Example 5 using the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex as a catalyst (the reaction solvent in Table 1 was methanol, and the amount of catalyst was 2 mol% with respect to the amine). The reaction solvent in Table 2 is water, and the amount of catalyst is 1 or 2 mol% with respect to the amine).
From the results of Tables 1 and 2, by using the catalyst comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex of the present invention, not only when using a non-aqueous solvent as a reaction solvent, but also when using water However, it was found that the reaction can proceed at room temperature, and 2-oxazolidinone can be obtained with good yield.

  The dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex of the present invention has various multiple bond additions such as production reactions of functional chemicals having a 2-oxazolidinone skeleton including pharmaceutical intermediates and antibiotics as catalysts. Applicable to reaction.

Claims (6)

Formula (I)

[Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Trifluoromethanesulfonyl) imidate ion. G is the general formula (II)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0. Here, n is 1, and those wherein R ¹ is alkyl group exclude)
Is a group represented by
And a dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex.   A catalyst for multiple bond addition reaction comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to claim 1.   A catalyst for producing 2-oxazolidinone comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to claim 1.   A catalyst for producing 2-oxazolidinone used in an aqueous solvent comprising the dendrimer-immobilized nitrogen-containing heterocyclic carbene-gold complex according to claim 1. Formula (III)

[Wherein X is a halogen atom, G is a general formula (II)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms, an aralkyl group having 7 carbon atoms, or an average of m represented by (CH ₂ CH ₂ O) _m CH ₃ = 1 to 20 alkoxy groups. .n represents an integer of 1 to 4 .d, of e and f, at least two in one and the other is 0. Here, n is 1, and those wherein R ¹ is alkyl group exclude)
Is a group represented by
A nitrogen-containing heterocyclic carbene producing step for producing a nitrogen-containing heterocyclic carbene in a solution by reacting a dendrimer-immobilized imidazolium salt represented by formula (I) with silver (I) oxide in a solvent;
A solution in which a dendrimer-immobilized nitrogen-containing heterocyclic carbene is formed;
AuL [S (CH ₃ ) ₂ ] (IV)
(Wherein L is a halide ion, trifluoromethanesulfonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoroacetic acid Ion, organic carboxylate ion, nitrate ion, hydrogen sulfate ion, tetrachloroiron (III) acid ion, tetrabromoiron (III) acid ion, toluenesulfonate ion, thiocyanate ion, cyanide ion, azide ion, or bis (Indicates (trifluoromethanesulfonyl) imidate ion)
A reaction step of mixing a gold (I) compound represented by the following composition and reacting in a solvent; and
A purification step comprising separating and purifying the product obtained in the reaction step by column chromatography using an eluent containing an ester solvent as a main component;
Comprising the general formula (I)

(In the formula, G and L have the same meaning as described above.)
The manufacturing method of the dendrimer fixed nitrogen-containing heterocyclic carbene-gold complex represented by these. In the presence of the catalyst according to any one of claims 2 to 4 and carbon dioxide, the general formula (VIII)

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or hydrocarbon groups, and when two or more of them are hydrocarbon groups, any two are bonded to each other to form a ring. May be formed)
Is reacted with propargylamine represented by the general formula (IX)

(Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above)
The 2-oxazolidinone represented by these is manufactured, The 2-oxazolidinone manufacturing method characterized by the above-mentioned.