JP4595111B2 - Alpha-glycol-encapsulated dendrimer, process for producing the same, alpha-glycol-type bidentate ligand and Lewis acid catalyst having the coordination structure - Google Patents

Description

  The present invention relates to a novel α-glycol-encapsulated dendrimer, a method for producing the same, an α-glycol type bidentate ligand composed of a certain kind of the dendrimer, and an aluminum-containing compound having a coordination structure thereof It relates to a Lewis acid catalyst.

  A dendrimer has a molecular structure branched like a tree from the central nucleus, and consists of a central part called a core, a branched repeating part called a dendron, and a terminal group, and can control the molecular structure and molecular size to a high degree. It is a possible polymer compound. Focusing on this unique structure, in recent years, it has been attempted to use it as a functional polymer by introducing functional groups into various parts of the dendrimer (see Non-Patent Document 1).

  One of them is to provide a dendrimer with a catalytic function, and many dendrimer-immobilized catalysts have been developed so far, most of which have the catalyst immobilized on the outermost shell 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 ligand (see Non-Patent Document 4), derived from tartaric acid introduced into the core of the dendrimer. And a dendrimer-immobilized titanium alkoxide catalyst (see Non-Patent Document 5) using a chiral α-glycol bidentate ligand.

  In addition, it has recently been found that living polymerization proceeds smoothly by immobilizing a polymerization initiator on a dendrimer (see Non-Patent Documents 6 to 9). Therefore, the development of a simple method for producing a ligand-encapsulated dendrimer in which a ligand is introduced into the core portion of the dendrimer is demanded.

“Dendrimers and Dendrons”, 2001, p. 51 (WILEY-VCH) “The Journal of Synthetic Organic Chemistry”, 2000, Vol. 58, p. 988 “Chemical Industry”, 2001, Vol. 52, p. 933 “Nature”, 1994, 372, p. 659 “Chemistry-European Journal” (Chem. Eur. J.), Volume 5, 1999, p. 3221 “Journal of Polymer Science Part A” (J. Polym. Sci. Part A), 1999, vol. 37, p. 1923 "Journal of Polymer Science Part A (J. Polym. Sci. Part A)", 1998, Vol. 36, p. 1 “Macromolecules”, 1996, Vol. 29, p. 4167 “Journal of American Chemical Society (J. Am. Chem. Soc.)”, 1996, Vol. 118, p. 11111

  An object of the present invention is to provide an α-glycol skeleton in the core of a dendrimer, in which a certain kind of α-glycol type bidentate ligand used as a raw material for a Lewis acid catalyst is useful. It is an object to provide an α-glycol-encapsulated dendrimer having the formula:

  As a result of intensive studies on the above-mentioned α-glycol-encapsulated dendrimer, the present inventors have made a novel α-glycol-encapsulated type by reacting thioglycerol or dithiothreitol with a dendron having a specific structure in a solvent. Dendrimers can be easily obtained, and some of these α-glycol-encapsulated dendrimers can be used as bidentate ligands, and dendrimer-immobilized aluminum compounds prepared using these as ligands are: Since the organic reaction activated by the Lewis acid is efficiently promoted, it has been found useful as a novel Lewis acid catalyst, and the present invention has been completed based on these findings.

［式中、Ａは水素原子又は−ＣＨ_２−Ｓ−Ｇ〔ここでＧは一般式（ＩＩ）

（式中、Ｒ^１は炭素数１〜１０のアルキレン基、Ｘは水素原子、または、アルコキシ基、アルコキシカルボニル基、ヒドロキシル基、カルボキシル基、ナトリウムカルボキシレートまたはカリウムカルボキシレートで置換されていてもよい、炭素原子数１〜１０のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜２０のアラルキル基、ｐは１、ｑ、ｒ、ｓ及びｔはそれぞれ０、 ｎは１以上の整数、ｄ、ｅ及びｆのうち少なくとも２つが１、残りは０を示す）
で表される基である〕
で表される基である］
で表されるデンドリマーであることを特徴とするα‐グリコール内包型デンドリマー。
（２） 一般式（ＩＩＩ）

（式中、Ｒ^１は炭素数１〜１０のアルキレン基、Ｘは水素原子、または、アルコキシ基、アルコキシカルボニル基、ヒドロキシル基、カルボキシル基、ナトリウムカルボキシレートまたはカリウムカルボキシレートで置換されていてもよい、炭素原子数１〜１０のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜２０のアラルキル基、Ｔはハロゲン原子、ｐは１、ｑ、ｒ、ｓ及びｔはそれぞれ０、ｎは１以上の整数、ｄ、ｅ及びｆのうち少なくとも２つが１、残りは０を示す）
で表されるデンドロンと、一般式（ＩＶ）

（式中、Ｄは水素原子又は−ＣＨ_２ＳＨを示す）
で表されるメルカプタンとを塩基存在下溶媒中で反応させることを特徴とする一般式（Ｉ）

［式中、Ａは水素原子又は−ＣＨ_２−Ｓ−Ｇ〔ここでＧは一般式（ＩＩ）

（式中、Ｒ^１は炭素数１〜１０のアルキレン基、Ｘは水素原子、または、アルコキシ基、アルコキシカルボニル基、ヒドロキシル基、カルボキシル基、ナトリウムカルボキシレートまたはカリウムカルボキシレートで置換されていてもよい、炭素原子数１〜１０のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜２０のアラルキル基、ｐは１、ｑ、ｒ、ｓ及びｔはそれぞれ０、ｎは１以上の整数、ｄ、ｅ及びｆのうち少なくとも２つが１、残りは０を示す）
で表される基である〕
で表される基である］
で表されるα‐グリコール内包型デンドリマーの製造方法。
（３） 下記一般式（Ｖ）

［式中、Ａは水素原子又は−ＣＨ_２−Ｓ−Ｇ´〔ここでＧ´は一般式（ＩＩ´）

（式中、Ｒ^１は炭素数１〜１０のアルキレン基、Ｘ´は水素原子、または、アルコキシ基、アルコキシカルボニル基で置換されていてもよい、炭素原子数１〜１０のアルキル基、炭素数３〜８のシクロアルキル基、炭素数６〜１４のアリール基または炭素数７〜２０のアラルキル基、ｐは１、ｑ、ｒ、ｓ及びｔはそれぞれ０、ｎは１以上の整数、ｄ、ｅ及びｆのうち少なくとも２つが１、残りは０を示す）
で表される基である〕、Ｊはアルキル基、ｇは０、ｈは１を示す］
で表される含アルミニウムルイス酸触媒。 That is, according to the present invention, the following inventions are provided.
(1) General formula (I)

[In the formula, A is a hydrogen atom or —CH ₂ —S—G [where G is the general formula (II)

Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom, or may be substituted with an alkoxy group, alkoxycarbonyl group, hydroxyl group, carboxyl group, sodium carboxylate or potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, p is 1, q, r, s and t Is 0, n is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
It is a group represented by
Is a group represented by
An α-glycol-encapsulated dendrimer represented by the formula:
(2) General formula (III)

Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom, or may be substituted with an alkoxy group, alkoxycarbonyl group, hydroxyl group, carboxyl group, sodium carboxylate or potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, T is a halogen atom, p is 1, q, (r, s, and t are each 0, n is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
A dendron represented by the general formula (IV)

(Wherein D represents a hydrogen atom or —CH ₂ SH)
Wherein the mercaptan represented by the general formula (I) is reacted in the presence of a base in a solvent.

[In the formula, A is a hydrogen atom or —CH ₂ —S—G [where G is the general formula (II)

Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom, or may be substituted with an alkoxy group, alkoxycarbonyl group, hydroxyl group, carboxyl group, sodium carboxylate or potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, p is 1, q, r, s and t Is 0, n is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
It is a group represented by
Is a group represented by
The manufacturing method of the alpha-glycol inclusion type dendrimer represented by these.
(3) The following general formula (V)

[Wherein, A is a hydrogen atom or —CH ₂ —SG ′ [where G ′ is a general formula (II ′)

(Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X ′ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with an alkoxy group or an alkoxycarbonyl group, and the number of carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, p is 1, q, r, s and t are each 0, n is an integer of 1 or more, d, (At least two of e and f indicate 1 and the rest indicate 0)
J is an alkyl group, g is 0, and h is 1.]
An aluminum-containing Lewis acid catalyst represented by the formula:

［式中、Ａは水素原子又は−ＣＨ_２−Ｓ−Ｇ〔ここでＧは一般式（ＩＩ）

（式中、Ｒ^１、Ｒ^２及びＲ^３は２価炭化水素基、Ｘは水素原子または置換されていてもよい炭化水素基、Ｙ及びＺはＯ、Ｓ、ＮＱ（Ｑは水素原子又はアルキル基である）、ＳＯ、ＳＯ_２、エステル基、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す〕
で表される基である〕
で表される基である］ The novel α-glycol-encapsulating dendrimer of the present invention is represented by the general formula (I).

[In the formula, A is a hydrogen atom or —CH ₂ —S—G [where G is the general formula (II)

(Wherein R ¹ , R ² and R ³ are divalent hydrocarbon groups, X is a hydrogen atom or an optionally substituted hydrocarbon group, Y and Z are O, S, NQ (Q is a hydrogen atom or an alkyl group) A divalent linking group consisting of SO, SO ₂ , an ester group, an amide group or a carbonyl group, p, q, r, s and t are each 0 or 1, n is an integer of 1 or more, d, e And at least two of f indicate 1 and the rest indicate 0)
It is a group represented by
Is a group represented by

About this dendrimer, the structure shown by each code | symbol in the substituent in the said formula is demonstrated concretely, and the structure is further clarified.
(1) R ¹ , R ² and R ³ represent a divalent hydrocarbon group, and this group includes a divalent aliphatic group and a divalent aromatic group. Divalent aliphatic groups include chain and cyclic groups. The divalent aromatic group includes an arylene group and an aralkylene group.
Examples of the divalent aliphatic group include alkylene groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (for example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, isobutylene group, etc.), and 3 to 8 carbon atoms. , Preferably 5-6 cycloalkylene groups (for example, cyclopentylene group, cyclohexylene group, etc.) are mentioned.
Examples of the divalent aromatic group include arylene groups having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenylene group, naphthylene group, etc.), and aralkylene groups having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms. Examples include groups represented by general formula (VI).
_{^{- (R 4) u -Ar- (}} R 5) v - (VI)
(In the formula, Ar represents an arylene group, R ⁴ and R ⁵ represent a lower alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, u and v are 1 or 0, and one of these is 1)
(2) X is a hydrogen atom or an optionally substituted hydrocarbon group, and the hydrocarbon group includes an aliphatic group and an aromatic group. Aliphatic groups include chain and cyclic groups. Aromatic groups include aryl groups and aralkyl groups.
As the aliphatic group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group), or 3 to 8 carbon atoms, preferably Includes 5 to 6 cycloalkyl groups (for example, cyclopentyl group, cyclohexyl group and the like).
As the aromatic group, an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms, for example, a general formula And a group represented by (VII).
_{^{- (R 6) w -Ar '}} - (R 7) x -H (VII)
(In the formula, Ar ′ represents an arylene group, R ⁶ represents a lower alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and R ⁷ represents a lower alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. W and x are 1 or 0, and either one of these represents 1)
Further, the hydrocarbon group may be substituted, and examples of the substituent include a substituent inert to the reaction in the production of the α-glycol-encapsulated dendrimer, such as an alkoxy group, an alkoxycarbonyl group, and the like. Examples thereof include functional groups that can be easily converted from, for example, hydroxyl group, carboxyl group, sodium carboxylate, potassium carboxylate and the like.
(3) Y and Z are O, S, NQ (Q is a hydrogen atom or an alkyl group), a sulfinyl group (-SO-), a sulfonyl group _(-SO 2 -), ester group (-OCO -, - CO ₂ - ), An amide group [—NRCO—, —CONR— (R is a hydrogen atom or an alkyl group)] or a carbonyl group (—CO—), preferably O, S or a sulfonyl group (—SO ₂ —). .
(4) p, q, r, s and t each represent 0 or 1, but preferably p, q and r are 1 and s and t are 0, or p is 1 and q, r, s and t are 0.
(5) The generation number n of the repeating structure is an integer of 1 or more, preferably 2-9.
(6) Among d, e, and f, at least two indicate 1 and the remaining indicates 0.
As an example of the group represented by the symbol G, the case where any two of d, e and f are 1 and n = 3 is as follows.
_{^{- (R 1) p - (}} Y) q - (R 2) r - (Z) s - (R 3) t -C 6 H 3 - [O- (R 1) p - (Y) q - (R _{^{2) r - (Z) s}} - (R 3) t -C 6 H 3 - [O- (R 1) p - (Y) q - (R 2) r - (Z) s - (R 3) t _{-C 6 H 3 - (O-} X) 2] 2] 2

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｙ、Ｚ、ｄ、ｅ、ｆ、ｐ、ｑ、ｒ、ｓ及びｔは、前記と同じ意味を示す。）
この繰り返し構造として好ましくは、化１１中の各符号について、ｄ、ｆ及びｐが１、ｅ、ｑ、ｒ、ｓ及びｔが０、Ｒ^１がアルキレン基であるものが挙げられる。 In the dendrimer of the general formula (I), the repeating structure is represented by the general formula (VIII).

(In the formula, R ¹ , R ² , R ³ , Y, Z, d, e, f, p, q, r, s and t have the same meaning as described above.)
Preferred examples of this repeating structure include those in which d, f and p are 1, e, q, r, s and t are 0, and R ¹ is an alkylene group for each symbol in Chemical Formula 11.

（式中、Ｒ^１、Ｒ^２及びＲ^３は２価炭化水素基、Ｘは水素原子または置換されていてもよい炭化水素基、Ｙ及びＺはＯ、Ｓ、ＮＱ（Ｑは水素原子又はアルキル基である）、ＳＯ、ＳＯ_２、エステル基、アミド基又はカルボニル基から成る２価連結基、Ｔはハロゲン原子、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表されるデンドロンと、一般式（ＩＶ）

（式中、Ｄは水素原子又は−ＣＨ_２ＳＨを示す）
で表されるメルカプタンとを塩基存在下溶媒中で反応させることにより製造することができる。
この製法では、塩基とメルカプタンとの反応により生成したチオレートアニオンの、ハロゲン原子に隣接する炭素原子上での求核置換反応が進行するため、α−グリコール内包型デンドリマーが製造される。 The α-glycol-containing dendrimer of the present invention is produced by the following production method.
Formula (III)

(Wherein R ¹ , R ² and R ³ are divalent hydrocarbon groups, X is a hydrogen atom or an optionally substituted hydrocarbon group, Y and Z are O, S, NQ (Q is a hydrogen atom or an alkyl group) A divalent linking group comprising SO, SO ₂ , an ester group, an amide group or a carbonyl group, T is a halogen atom, p, q, r, s and t are each 0 or 1, and n is 1 or more (At least two of integers, d, e, and f indicate 1 and the rest indicate 0)
A dendron represented by the general formula (IV)

(Wherein D represents a hydrogen atom or —CH ₂ SH)
It can manufacture by making the mercaptan represented by these react with a solvent in presence of a base.
In this production method, a nucleophilic substitution reaction on the carbon atom adjacent to the halogen atom of the thiolate anion generated by the reaction between the base and the mercaptan proceeds, so that an α-glycol-encapsulated dendrimer is produced.

The structure of R ¹ , R ² , R ³ , X, Y, Z of the dendron represented by the general formula (III) and the number of d, e, f, n, p, q, r, s, t are As in the case of the dendrimer represented by the general formula (I), X is a hydrocarbon group or a hydrocarbon group substituted with an alkoxy group or an alkoxycarbonyl group. Since the group is inactive to the reaction, the desired reaction proceeds smoothly, which is preferable.

Examples of the base to be used include hydroxides such as sodium hydroxide and potassium hydroxide, among which sodium hydroxide is preferable.
As the reaction solvent, those which can dissolve dendron, mercaptan and base and do not participate in the reaction are used. Specifically, halogenated hydrocarbons such as ethanol, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, diethyl ether, hydrocarbon, dichloromethane and the like are preferable, and these solvents are used alone or in the form of a composite solvent. Among them, a preferable reaction solvent is a composite solvent of ethanol and tetrahydrofuran.
When performing the reaction between dendron and mercaptan using this solvent, it is preferable to first dissolve the mercaptan in a solution in which a base is dissolved in a solvent under a nitrogen atmosphere, and then add the dendron to the solution. With stirring.

Regarding the reaction conditions, the reaction temperature is preferably in the range of room temperature to 100 ° C., and the reaction time varies depending on other conditions such as the reaction temperature and the solvent to be used and cannot be determined unconditionally. About 24 hours.
Further, the use ratio of dendron and mercaptan is not necessarily limited, but is generally in the range of 1 to 3 mol, preferably 1 to 1.3 mol, per mol of mercapto group contained in the mercaptan. The dendron 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 α-glycol-containing dendrimer can be produced in one step.

（式中Ｒ^８、Ｒ^９及びＪは、炭化水素基、Ｌはハロゲン原子、ｇ及びｈはいずれか一方は１で他方が０を示す）
で表されるアルミニウム化合物を、溶媒の存在下に反応させ、一般式（Ｖ）

［式中、Ａは水素原子又は−ＣＨ_２−Ｓ−Ｇ´〔ここでＧ´は一般式（ＩＩ´）

（式中、Ｒ^１、Ｒ^２及びＲ^３は２価炭化水素基、Ｘ´はアルコキシ基またはアルコキシカルボニル基で置換されていてもよい炭化水素基、Ｙ及びＺはＯ、Ｓ、ＮＱ（Ｑは水素原子又はアルキル基である）、ＳＯ、ＳＯ_２、エステル基、アミド基又はカルボニル基から成る２価連結基、ｐ、ｑ、ｒ、ｓ及びｔはそれぞれ０又は１、ｎは１以上の整数、ｄ、ｅ及びfのうち少なくとも２つが１、残りは０を示す）
で表される基である〕、Ｊは炭化水素基、Ｌはハロゲン原子、ｇ及びｈはいずれか一方が１で他方は０を示す］
で表される、デンドリマーコア部のα−グリコールを二座配位子とするアルミニウム化合物を製造することができる。
上記Ｌで示されるハロゲン原子は特に限定されず、フッ素、塩素、臭素、ヨウ素等が挙げられ、また、上記Ｊで示される炭化水素基は特に限定されず、アルキル基、アルケニル基、シクロアルキル基、アリール基、アラルキル基等が挙げられる。 Among the α-glycol-encapsulated dendrimers represented by the general formula (I) of the present invention, those in which X is a hydrocarbon group optionally substituted with an alkoxy group or an alkoxycarbonyl group are obtained by coordination to a metal. In order to construct a stable 5-membered ring structure, it can be used as a bidentate ligand. One example of the reaction with the metal compound using the α-glycol-encapsulated dendrimer as a bidentate ligand will be described below.
Under nitrogen atmosphere, α-glycol-encapsulated dendrimer as the bidentate ligand and the general formula (IX)

(Wherein R ⁸ , R ⁹ and J are hydrocarbon groups, L is a halogen atom, g and h are either 1 and the other is 0)
The aluminum compound represented by general formula (V) is reacted in the presence of a solvent.

[Wherein, A is a hydrogen atom or —CH ₂ —SG ′ [where G ′ is a general formula (II ′)

(Wherein R ¹ , R ² and R ³ are divalent hydrocarbon groups, X ′ is a hydrocarbon group which may be substituted with an alkoxy group or an alkoxycarbonyl group, Y and Z are O, S, NQ (Q Is a hydrogen atom or an alkyl group), a divalent linking group comprising SO, SO ₂ , an ester group, an amide group or a carbonyl group, p, q, r, s and t are each 0 or 1, and n is 1 or more (At least two of integers, d, e, and f indicate 1 and the rest indicate 0)
J is a hydrocarbon group, L is a halogen atom, g and h are either 1 and the other is 0]
The aluminum compound which uses (alpha) -glycol of a dendrimer core part represented by these as a bidentate ligand can be manufactured.
The halogen atom represented by L is not particularly limited, and examples thereof include fluorine, chlorine, bromine, iodine, etc. The hydrocarbon group represented by J is not particularly limited, and may be an alkyl group, an alkenyl group, a cycloalkyl group. , Aryl group, aralkyl group and the like.

This reaction is carried out by dissolving a predetermined α-glycol-containing dendrimer in a solvent and dropping a hydrocarbon solution of an aluminum compound. The solvent is usually an organic solvent, preferably a hydrocarbon solvent such as toluene or hexane.
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 product was obtained by distilling off the solvent under reduced pressure. The production of the target product was confirmed by ¹ H-NMR measurement. This result shows that the α-glycol-encapsulated dendrimer has a novel bidentate configuration. Indicates that it is a rank.

  Thus, the aluminum compound is immobilized by coordination with the dendrimer as a bidentate ligand. This dendrimer-immobilized aluminum compound is applied to organic reactions activated by various Lewis acid catalysts, such as carbon-carbon bond formation reactions such as aldol reaction and Diels-Alder reaction, and ring-opening polymerization reactions of lactones. Since the reaction can be promoted, it is useful as a Lewis acid catalyst.

（式中、ｊは０以上１２以下の整数を示す）
で表されるラクトンを、溶媒の存在下に反応させ、一般式（ＸＩ）

（式中、ｊは前記と同じ意味を示し、ｋは重合度を示す）
で表されるポリエステルを製造することができる。 One example of the reaction using the dendrimer-immobilized aluminum compound represented by the general formula (V) of the present invention as such a Lewis acid catalyst will be described below.
In the presence of the dendrimer-immobilized aluminum compound as the catalyst, the compound represented by the general formula (X)

(Where j represents an integer from 0 to 12)
A lactone represented by the formula (XI) is reacted in the presence of a solvent.

(Wherein j represents the same meaning as described above, and k represents the degree of polymerization)
Can be produced.

This reaction is performed by dissolving and adding the raw material and the catalyst in a solvent. The solvent is usually an organic solvent, preferably dichloromethane, acetonitrile, toluene or the like.
The reaction can usually proceed at about room temperature, but may be promoted by heating. During the reaction, the reaction solution is preferably stirred.
After completion of the reaction, the reaction solution is concentrated, dissolved in chloroform, and added dropwise to methanol to precipitate the target product. After adding a hydrochloric acid-methanol solution, the target material can be obtained by filtration.

  Since the Lewis acid catalyst of the present invention has a dendrimer-immobilized structure, since the mutual association between aluminum is suppressed, for example, the reactivity is higher than triisopropoxyaluminum, which is a general-purpose catalyst, and the vicinity of the reaction point is three-dimensional. In addition, since it is bulky and transesterification is suppressed, a polyester having a low degree of dispersion (Mw / Mn) is obtained, which is useful as a new dendrimer type living polymerization catalyst.

  As described above, the dendrimer-immobilized aluminum compound represented by the general formula (V) is useful as a Lewis acid catalyst, and in particular, by using this catalyst, a ring-opening polymerization reaction of lactone can be efficiently performed in a solvent. Can be promoted.

  According to the present invention, a novel α-glycol-encapsulated dendrimer can be obtained, and some of these compounds are useful as bidentate ligands. An aluminum compound having this as a bidentate ligand is effective as a Lewis acid catalyst, and contributes to efficient progress of a chemical reaction in an organic solvent, for example, an organic reaction such as ring-opening polymerization of a lactone.

  Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.

Under a nitrogen atmosphere, sodium hydroxide 12.3 mg in ethanol (5 ml), thioglycerol 39 mg in tetrahydrofuran (2 ml) and 3,5-bis [3,5-bis (benzyloxy) benzyloxy] benzyl bromide 170 at room temperature .8 mg of tetrahydrofuran solution (2 ml) was sequentially added and stirred for 2 hours.
Subsequently, the solvent was distilled off from the reaction solution under reduced pressure, and the resulting crude product was purified by silica gel chromatography (toluene: ethyl acetate = 3: 1) (white powder, yield 175.4 mg, yield 99.). 4%).
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, CDCl ₃ ) δ / ppm 7.42-7.28 (m, 20H), 6.68-6.47 (m, 9H), 5.01 (s, 8H), 4. 94 (s, 4H), 3.71-3.65 (m, 1H), 3.63 (s, 2H), 3.63-3.58 (m, 1H), 3.46-3.40 ( m, 1H), 2.67 (d, 1H, J = 3.7 Hz), 2.56-2.44 (m, 2H), 2.05 (t, 1H, J = 6.1 Hz)
From these analysis results, this product was identified as a compound represented by the following structural formula.

Under a nitrogen atmosphere, sodium hydroxide 91.7 mg in ethanol (4 ml), DL-dithiothreitol 159.7 mg in tetrahydrofuran (2 ml) and 3,5-dibenzyloxybenzyl bromide 873.3 mg in tetrahydrofuran at room temperature The solution (3 ml) was added sequentially and stirred for 2 hours.
Subsequently, the solvent was distilled off from the reaction solution under reduced pressure, and the resulting crude product was purified by silica gel chromatography (toluene: ethyl acetate = 10: 1) (white powder, yield 600.8 mg, yield 76.). 5%).
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, CDCl ₃ ) δ / ppm 7.40-7.24 (m, 20H), 6.57-6.50 (m, 6H), 4.99 (s, 8H), 4. 94 (s, 4H), 3.63 (s, 4H), 3.63-3.57 (m, 2H), 2.62-2.52 (m, 6H)
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表されるデンドロン７３３．８ｍｇのテトラヒドロフラン溶液（１０ｍｌ）を順次加え、２時間攪拌した。
次いで、反応液を減圧下で溶媒を留去し、得られた粗生成物をシリカゲルクロマトグラフィー（トルエン：酢酸エチル＝４：１）で精製した（白色粉末、収量６６１．６ｍｇ、収率９６．１％）。
このものの核磁気共鳴スペクトル分析結果は次の通りである。
^１Ｈ−ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）δ／ｐｐｍ ６．６５−６．３８（ｍ，４２Ｈ），４．９２（ｓ，１６Ｈ），４．９０（ｓ，８Ｈ），３．７６（ｓ，４８Ｈ），３．６１（ｂｒｓ，６Ｈ），２．６１−２．５２（ｍ，４Ｈ）
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であると同定された。

Under a nitrogen atmosphere, sodium hydroxide 36.0 mg in ethanol solution (3 ml), DL-dithiothreitol 50.9 mg in tetrahydrofuran solution (5 ml) and the following structural formula

A tetrahydrofuran solution (10 ml) of dendron 733.8 mg represented by the above was sequentially added and stirred for 2 hours.
Subsequently, the solvent was distilled off from the reaction solution under reduced pressure, and the resulting crude product was purified by silica gel chromatography (toluene: ethyl acetate = 4: 1) (white powder, yield 661.6 mg, yield 96.). 1%).
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, CDCl ₃ ) δ / ppm 6.65-6.38 (m, 42H), 4.92 (s, 16H), 4.90 (s, 8H), 3.76 (s, 48H), 3.61 (brs, 6H), 2.61-2.52 (m, 4H)
From these analysis results, this product was identified as a compound represented by the following structural formula.

で表される含アルミニウム化合物であることが確認された。 Under a nitrogen atmosphere, 0.1 ml of a 0.31 M diethylaluminum ethoxide / toluene solution was slowly added dropwise at 0 ° C. to an anhydrous toluene solution (1.5 ml) of the α-glycol-encapsulated dendrimer obtained in Example 3 Then, after stirring at room temperature for 2 hours, the reaction solvent was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 3 hours. The yield was 70.7 mg.
The result of nuclear magnetic resonance spectrum analysis of this product is as follows.
¹ H-NMR (500 MHz, C ₆ D ₅ CD ₃ ) δ / ppm 6.74-6.35 (m, 42H), 4.73 (brs, 24H), 3.39 (brs, 48H), 0. 97 (brs, 3H)
From these analysis results, this product is represented by the formula (XII)

It was confirmed that it is an aluminum-containing compound represented by.

ＧＰＣカラム（東ソー、ＴＳＫｇｅｌ ＧＭＨＸＬ−Ｌ ２本）を用いた高速液体クロマトグラフ分析より、数平均分子量Ｍｎ２１０００、分散度Ｍｗ／Ｍｎ１．１６（標準ポリスチレン換算）であることが分かった。
Under a nitrogen atmosphere, 0.17 ml of 1.57M diethylaluminum ethoxide / toluene solution was slowly added dropwise at 0 ° C. to 323.8 mg of anhydrous α-glycol-encapsulated dendrimer obtained in Example 3 (3 ml), By stirring at room temperature for 2 hours, an aluminum-containing Lewis acid catalyst comprising an aluminum-containing compound of the formula (XII) was prepared.
An anhydrous toluene solution (3 ml) of this aluminum-containing Lewis acid catalyst was slowly added dropwise at 0 ° C. under a nitrogen atmosphere to 1.678 g of anhydrous toluene solution (10 ml) and stirred at room temperature for 1 hour.
After completion of the reaction, the reaction solution is concentrated, dissolved in a small amount of chloroform, and added dropwise to methanol (500 ml) to precipitate the target product. To this, 10% hydrochloric acid-methanol solution (10 ml) is added, and overnight at room temperature. After allowing to stand, filtration, washing, and vacuum drying at 40 ° C. for 12 hours, poly (ε-caprolactone) having the following structural formula was obtained (yield 94%).

From the high performance liquid chromatograph analysis using the GPC column (Tosoh, TSKgel GMHXL-L 2), it turned out that it is number average molecular weight Mn21000 and dispersion degree Mw / Mn1.16 (standard polystyrene conversion).

Claims (3)

Formula (I)

[In the formula, A is a hydrogen atom or —CH ₂ —S—G [where G is the general formula (II)

( Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom , or may be substituted with an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, a carboxyl group, a sodium carboxylate or a potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms , p is 1 , q, r, s and t Is 0 , n is an integer of 1 or more, at least two of d, e and f are 1, and the rest are 0)
It is a group represented by
Is a group represented by
An α-glycol-encapsulated dendrimer represented by the formula: Formula (III)

( Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom , or may be substituted with an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, a carboxyl group, a sodium carboxylate or a potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, T is a halogen atom, p is 1 , q, (r, s, and t are each 0 , n is an integer of 1 or more, at least two of d, e, and f are 1, and the rest are 0)
A dendron represented by the general formula (IV)

(Wherein D represents a hydrogen atom or —CH ₂ SH)
Wherein the mercaptan represented by the general formula (I) is reacted in the presence of a base in a solvent.

[In the formula, A is a hydrogen atom or —CH ₂ —S—G [where G is the general formula (II)

( Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X is a hydrogen atom , or may be substituted with an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, a carboxyl group, a sodium carboxylate or a potassium carboxylate. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms , p is 1 , q, r, s and t Is 0 , n is an integer of 1 or more, at least two of d, e and f are 1, and the rest are 0)
It is a group represented by
Is a group represented by
The manufacturing method of the alpha-glycol inclusion type dendrimer represented by these. The following general formula (V)

[Wherein, A is a hydrogen atom or —CH ₂ —SG ′ [where G ′ is a general formula (II ′)

Wherein R ¹ is an alkylene group having 1 to 10 carbon atoms, X ′ is a hydrogen atom , an alkyl group having 1 to 10 carbon atoms which may be substituted with an alkoxy group or an alkoxycarbonyl group, and carbon number. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 20 carbon atoms , p is 1 , q, r, s and t are each 0 , n is an integer of 1 or more, d, (At least two of e and f indicate 1 and the rest indicate 0)
J is an alkyl group, g is 0, and h is 1. ]
An aluminum-containing Lewis acid catalyst represented by the formula: