JP2002531457A - Method for producing cross-linked tetraaza macrocycles - Google Patents

Method for producing cross-linked tetraaza macrocycles

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Publication number
JP2002531457A
JP2002531457A JP2000585243A JP2000585243A JP2002531457A JP 2002531457 A JP2002531457 A JP 2002531457A JP 2000585243 A JP2000585243 A JP 2000585243A JP 2000585243 A JP2000585243 A JP 2000585243A JP 2002531457 A JP2002531457 A JP 2002531457A
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Japan
Prior art keywords
ligand
mixtures
formula
methyl
independently
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Japanese (ja)
Inventor
ジョージ、ダグラス、ヒラー、ザ、セカンド
クリストファー、マーク、パーキンズ
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
    • C07F13/005—Compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—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
    • 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
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/96—Water

Abstract

(57)【要約】 本発明は、約４０〜約１００℃の温度で、少くとも約１０のｐＨを有する水溶液中、パラジウム触媒の存在下で、ジ四級システトラサイクル前駆体を水素と接触させることにより、式（Ｉ）を有する架橋テトラアザ大環式リガンド（各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２）ｘＣＯ２Ｍおよびそれらの混合物である；但しＲ単位が双方ともメチルであることはない；Ｍは水素または塩形成カチオンである；ｘは１〜６である；各インデックスｎは独立して０〜３である）を製造するためのプロセスに関する。 (57) The present invention relates to contacting a diquaternary cis-tetracycle precursor with hydrogen in an aqueous solution having a pH of at least about 10 at a temperature of about 40 to about 100 ° C in the presence of a palladium catalyst. To form a bridged tetraaza macrocyclic ligand having formula (I) wherein each R is independently C 1 -C 8 straight or branched alkyl, — (CH 2 ) x CO 2 M and mixtures thereof; Wherein both R units are not methyl; M is hydrogen or a salt-forming cation; x is 1-6; each index n is independently 0-3). About.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の分野】FIELD OF THE INVENTION

本発明は架橋テトラアザマクロサイクル類を製造するための改良されたプロセ
スに関し、そのマクロサイクル類は遷移金属錯体を製造する上で有用なリガンド
として適している。本発明は、ここで記載された架橋マクロサイクル類の工業的
および他の商業的製造での使用によく適したプロセスを提供する。The present invention relates to an improved process for making bridged tetraaza macrocycles, which macrocycles are suitable as ligands useful in making transition metal complexes. The present invention provides a process that is well suited for use in the industrial and other commercial manufacture of the crosslinked macrocycles described herein.

【０００２】[0002]

【発明の背景】BACKGROUND OF THE INVENTION

テトラアザマクロサイクル類、例えばサイクラム(cyclam)は、多くの手法で製
造されてきたが、しかしながら、特に遷移金属触媒、とりわけブリーチ触媒の分
野で、リガンドとして広い用途が最近みいだされた架橋テトラアザマクロサイク
ル類、特にビスＮ‐置換テトラアザマクロサイクル類、とりわけ５，１２‐ジア
ルキル‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６．２〕ヘキサデカン類
の製造に関しては情報不足である。Tetraaza macrocycles, such as cyclam, have been prepared in a number of ways, however, particularly in the field of transition metal catalysts, especially bleach catalysts, crosslinked tetraaza macrocycles have recently found widespread use as ligands. Lack of information on the preparation of macrocycles, especially bis N-substituted tetraaza macrocycles, especially 5,12-dialkyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecanes .

【０００３】 ＷＯ９８／３９３３５Ａ１“架橋マクロポリサイクル類の改良された製造方法
”では、工業的スケールアップに必要な高収率を得やすい、架橋大多環式リガン
ド(cross-bridged macropolycyclic ligands)を製造するための合理的操作につ
いて開示している。しかしながら、ビシクロ架橋環形成をもたらす還元環開裂ス
テップでは、水素化ホウ素還元剤を利用している。このタイプの還元剤は業者に
制約を課すことがある。例えば、後処理でアミン／水素化ホウ素錯体を分解する
必要性、並びにホウ素廃棄物の適正な回収および処分は、そのプロセスのコスト
を上げる。しかも、過剰の水素化ホウ素が必要とされるならば、これには酸の使
用および多量の水素ガスの発生を伴う中和を要する。[0003] WO 98/39335 A1 "Improved Process for the Production of Cross-Linked Macropolycycles" produces cross-bridged macropolycyclic ligands which are easy to obtain the high yields required for industrial scale-up. For rational operation. However, the reductive ring cleavage step that results in bicyclo bridged ring formation utilizes a borohydride reducing agent. This type of reducing agent may place restrictions on the trader. For example, the need to decompose the amine / borohydride complex in post-treatment, and proper recovery and disposal of boron waste increases the cost of the process. Moreover, if an excess of borohydride is required, this requires the use of acids and neutralization with the generation of large amounts of hydrogen gas.

【０００４】 したがって、連続フロープロセスまたはバッチ製造に適用しうる、架橋大多環
式リガンドを製造するための高度に定量的な、好ましくは触媒プロセスに関して
、ニーズが存在する。[0004] Therefore, a need exists for a highly quantitative, preferably catalytic, process for producing bridged macropolycyclic ligands applicable to continuous flow processes or batch production.

【０００５】[0005]

【発明の要旨】[Summary of the Invention]

本発明は、選択されたビスＮ‐置換テトラアザマクロサイクル類が接触水素添
加により架橋大多環式リガンドへ変換されうることが意外にもわかったという点
で、前記ニーズを満たしている。The present invention fulfills that need in that it has been surprisingly found that selected bis N-substituted tetraaza macrocycles can be converted to bridged macropolycyclic ligands by catalytic hydrogenation.

【０００６】 本発明の第一面は、下記式を有するテトラアザ大環式リガンドを製造するため
のプロセスに関する：[0006] A first aspect of the present invention relates to a process for producing a tetraaza macrocyclic ligand having the formula:

【化１２】 （上記式中各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２）ｘ ＣＯ２Ｍおよびそれらの混合物であり、好ましくはＲ単位の双方がメチルである
ことはない；Ｍは水素または塩形成カチオンである；ｘは１〜６である；各イン
デックスｎは独立して０〜３である）； そのプロセスは： ａ）下記式を有するテトラアザ大環式リガンド前駆体：Embedded image (Wherein each R is independently C 1 -C 8 straight or branched alkyl, — (CH 2 ) x CO 2 M and mixtures thereof, preferably both R units are not methyl M is hydrogen or a salt-forming cation; x is 1-6; each index n is independently 0-3); the process is: a) a tetraaza macrocyclic ligand precursor having the formula: :

【化１３】 （上記式中Ｘ−は電荷中性をもたらすアニオンである）を、少くとも８のｐＨで
、約１ｐｐｍ以上の遷移金属水素添加触媒で水素添加して、テトラアザ大環式リ
ガンドを形成し；および ｂ）場合により、上記のリガンドを単離する ステップからなる。Embedded image (Wherein X − is an anion providing charge neutrality) at a pH of at least 8 with at least about 1 ppm of a transition metal hydrogenation catalyst to form a tetraaza macrocyclic ligand; and b) optionally, isolating the above ligand.

【０００７】 これらおよび他の目的、特徴および利点は、以下の詳細な記載および添付され
た請求の範囲を読むことで、当業者に明らかとなるであろう。ここですべてのパ
ーセンテージ、比率および割合は、別記されないかぎり重量による。すべての温
度は、別記されないかぎり摂氏度（℃）である。引用されたすべての文献は、関
連箇所で、参考のためここに組み込まれる。[0007] These and other objects, features and advantages will become apparent to those skilled in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius (° C) unless otherwise noted. All references cited are, in relevant places, incorporated herein by reference.

【０００８】[0008]

【発明の具体的な説明】DETAILED DESCRIPTION OF THE INVENTION

本発明は、下記式を有するテトラアザマクロサイクル類の接触水素添加に関す
る：The present invention relates to the catalytic hydrogenation of tetraaza macrocycles having the formula:

【化１４】 上記においてＮ置換四級環窒素と橋状炭素との共有結合が壊され、下記式を有す
る架橋大環式リガンド：Embedded image In the above, the covalent bond between the N-substituted quaternary ring nitrogen and the bridged carbon is broken, and the bridged macrocyclic ligand having the formula:

【化１５】 が得られる生成物となる。Embedded image Is obtained.

【０００９】 上記式中、各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２） ｘ ＣＯ２Ｍおよびそれらの混合物であり、好ましくはＲ単位の双方がメチルであ
ることはない；更に好ましくは一方のＲ単位はメチルで、他方のＲ単位はエチル
、プロピル、ブチル、ペンチル、ヘキシルおよびそれらの混合物からなる群より
選択される；メチル／アルキルＲ単位混合物のうち、好ましくは一方のＲはメチ
ルで、他方のＲはエチルまたはプロピルである。最も好ましいリガンドは、一方
のＲ単位がメチルで、他方のＲ単位がエチルである単位からなる。好ましいリガ
ンドは、各Ｒ単位がエチルであるマクロサイクル環である。Ｍは水素または塩形
成カチオンであり、その非制限例はナトリウム、カリウム、カルシウム、アンモ
ニウムである。Ｒが‐（ＣＨ２）ｘＣＯ２Ｍであるとき、インデックスｘは１〜
約６の値であり、好ましくはｘは１である。インデックスｎがマクロサイクル環
の大きさを決める。インデックスｎは０〜約３の値を有している。好ましいマク
ロサイクル環では、下記一般式のように、相対する１組のｎインデックスが１で
、他組のｎインデックスが０である：In the above formula, each R is independently C1-C8Linear or branched alkyl,-(CH2) x CO2M and mixtures thereof, preferably both R units are methyl
More preferably one R unit is methyl and the other R unit is ethyl
From the group consisting of, propyl, butyl, pentyl, hexyl and mixtures thereof
Selected; of the methyl / alkyl R unit mixture, preferably one R is methyl
And the other R is ethyl or propyl. The most preferred ligands are
Is a unit in which the R unit is methyl and the other R unit is ethyl. Preferred Riga
Is a macrocycle ring in which each R unit is ethyl. M is hydrogen or salt form
Non-limiting examples are sodium, potassium, calcium, and ammonium.
Nium. R is-(CH2)xCO2When M, the index x is 1 to
It has a value of about 6, and preferably x is 1. Index n is a macrocycle ring
Determine the size of The index n has a value of 0 to about 3. Preferred Mac
In a rocycle ring, as shown in the following general formula, a pair of opposing n indexes is 1 and
, The n index of the other set is 0:

【化１６】 上記式中Ｒは前記と同義である。Embedded image In the above formula, R has the same meaning as described above.

【００１０】 本発明による好ましいリガンドは、メチルおよびエチル、ジエチル、メチルお
よびプロピル、エチルおよびプロピル、メチルおよびブチル、エチルおよびブチ
ル、およびそれらの混合物からなる群より選択されるＲ単位対を有している。A preferred ligand according to the present invention has an R unit pair selected from the group consisting of methyl and ethyl, diethyl, methyl and propyl, ethyl and propyl, methyl and butyl, ethyl and butyl, and mixtures thereof. I have.

【００１１】 本発明のプロセスの出発物質は、テトラアザ大環式リガンド前駆体、または下
記式を有するビス四級システトラサイクル類である：The starting material for the process of the present invention is a tetraaza macrocyclic ligand precursor or bisquaternary cis tetracycles having the formula:

【化１７】 上記式中Ｒおよびｎは前記と同義である。Ｘは、ビス四級システトラサイクルに
電気的中性をもたらすように働くアニオンである。当業者は、“電気的中性”と
いう用語が“分子電荷バランス要件を満たす十分量のアニオン種”に関し、１、
２、３荷電種などの混合物もここでは用いてよい、と理解している。Ｘは好まし
くは単位負電荷を有しており、例えばハロゲン、トシレート、メチルサルフェー
ト、エチルサルフェートである。しかしながら、Ｘは二価以上の負電荷を有した
、例えばサルフェートでもよく、その場合に業者は単位負電荷アニオンを用いた
ときに要する量の半分のみで済む。好ましいＸはクロリド、ブロミド、ヨージド
、サルフェート、エチルサルフェート、メチルサルフェート、トシレート、メシ
レート、トリフレートおよびそれらの混合物である。Embedded image In the above formula, R and n are as defined above. X is an anion that serves to provide electrical neutrality to the bis-quaternary cis-tetracycle. One skilled in the art will recognize that the term "electroneutral" refers to "sufficient anionic species that meet molecular charge balance requirements",
It is understood that mixtures of a few charged species may also be used here. X preferably has a unit negative charge, for example, halogen, tosylate, methyl sulfate, ethyl sulfate. However, X may be a divalent or more negatively charged, for example sulfate, in which case the trader only needs half the amount required when using unit negatively charged anions. Preferred X is chloride, bromide, iodide, sulfate, ethyl sulfate, methyl sulfate, tosylate, mesylate, triflate and mixtures thereof.

【００１２】ステップ（ａ）水素添加‐還元開裂 ステップ（ａ）は、下記スキームで示されるような、触媒水素添加による還元
開裂からなる： Step (a) Hydrogenation-Reduction Cleavage Step (a) consists of reductive cleavage by catalytic hydrogenation, as shown in the following scheme:

【化１８】 上記ではシス‐テトラサイクルビス四級塩が架橋テトラアザマクロサイクルに変
換される。Embedded image In the above, the cis-tetracycle bis quaternary salt is converted to a bridged tetraaza macrocycle.

【００１３】 ステップ（ａ）は触媒、好ましくは担持触媒の存在下で行われる。触媒の非制
限例には、白金担持炭素、パラジウム担持炭素（Ｐｄ／Ｃ）、水酸化パラジウム
担持炭素（Ｐｄ（ＯＨ）２／Ｃ）、ロジウム担持炭素（Ｒｈ／Ｃ）、ラネーニッ
ケルおよびそれらの混合物がある。好ましい触媒はＰｄ（ＯＨ）２／Ｃである。
担持触媒は約１〜約５０重量％の遷移金属を含むが、しかしながら純金属、即ち
パラジウムは“担体”、即ち炭素の必要性なしに用いてもよい。触媒の“触媒量
”はステップ（ａ）の還元を行う上で十分な程度である。本発明の目的にとり、
触媒量という用語は“５重量％遷移金属触媒で約１ｐｐｍ以上”として定義され
る。しかしながら、業者は、反応生成物による触媒表面への毒性のため、触媒量
以上の触媒を用いてもよい。本発明のステップ（ａ）で用いられる触媒の量は、
好ましくは、約５〜５０重量％の遷移金属を含有した触媒で約１０ｐｐｍ以上、
遷移金属担持触媒で更に好ましくは約１００ｐｐｍ以上、更に一層好ましくは約
０．１重量％以上である。０．１重量％の遷移金属担持触媒（その触媒は、例え
ば、炭素上に１０重量％パラジウムを含んでいる）を含有した反応液は、０．０
１％遷移金属または１００ｐｐｍ遷移金属を存在させている。Step (a) is performed in the presence of a catalyst, preferably a supported catalyst. Non-limiting examples of catalysts include platinum on carbon, palladium on carbon (Pd / C), palladium hydroxide on carbon (Pd (OH) 2 / C), rhodium on carbon (Rh / C), Raney nickel and mixtures thereof. There is. The preferred catalyst is Pd (OH) 2 / C.
The supported catalyst contains from about 1 to about 50% by weight of the transition metal, however, a pure metal, ie, palladium, may be used without the need for a “support”, ie, carbon. The "catalytic amount" of the catalyst is sufficient to effect the reduction in step (a). For the purposes of the present invention,
The term catalytic amount is defined as "greater than about 1 ppm at 5 wt% transition metal catalyst". However, traders may use more catalyst than catalyst due to the toxicity of the reaction products to the catalyst surface. The amount of catalyst used in step (a) of the present invention is
Preferably, about 10 ppm or more of a catalyst containing about 5 to 50% by weight of a transition metal,
More preferably at least about 100 ppm, even more preferably at least about 0.1% by weight of the transition metal supported catalyst. A reaction solution containing 0.1% by weight of a transition metal-supported catalyst (for example, the catalyst contains 10% by weight of palladium on carbon) is 0.0% by weight.
1% transition metal or 100 ppm transition metal is present.

【００１４】 本発明のステップ（ａ）で存在する水素ガスの量は、触媒表面を十分に飽和し
さえすればよく、好ましくは水素圧は２００ｐｓｉ、更に好ましくは４００ｐｓ
ｉ、最も好ましくは８００ｐｓｉから、約２０００ｐｓｉ、更に好ましくは１０
００ｐｓｉまでである。The amount of hydrogen gas present in step (a) of the present invention only needs to sufficiently saturate the catalyst surface, preferably the hydrogen pressure is 200 psi, more preferably 400 ps
i, most preferably from 800 psi to about 2000 psi, more preferably 10 psi
Up to 00 psi.

【００１５】 本プロセスのステップ（ａ）は、２０℃、好ましくは約４０℃、更に好ましく
は約６０℃から、約１００℃、好ましくは約９０℃、更に好ましくは約８０℃、
最も好ましくは約６５℃までの温度で行える。[0015] Step (a) of the process comprises from 20 ° C, preferably about 40 ° C, more preferably from about 60 ° C to about 100 ° C, preferably about 90 ° C, more preferably about 80 ° C,
Most preferably at temperatures up to about 65 ° C.

【００１６】 ステップ（ａ）が行われるべきｐＨは、少くとも８、好ましくは少くとも１０
、更に好ましくは少くとも約１１である。好ましくは、ｐＨを調整するために用
いられる塩基は水溶液の形をとる。好ましい塩基は、、炭酸カリウム、炭酸ナト
リウム、水酸化ナトリウム、水酸化カリウムおよびそれらの混合物からなる群よ
り選択される。非制限例として、ｐＨを所要レベルへ調整するために十分量の１
Ｍ（モル）水性塩基を用いれば、それでよい。好都合な好ましい塩基は炭酸カリ
ウムである。The pH at which step (a) is to be carried out is at least 8, preferably at least 10
, More preferably at least about 11. Preferably, the base used to adjust the pH is in the form of an aqueous solution. Preferred bases are selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide and mixtures thereof. As a non-limiting example, a sufficient amount of 1 to adjust the pH to the required level
If an M (mole) aqueous base is used, that is sufficient. A convenient and preferred base is potassium carbonate.

【００１７】 適切な代替法として、ステップ（ａ）は水以外の溶媒の存在下または水の不在
下で行ってもよい。適切な溶媒および水の混合液も、本発明の水素添加プロセス
を行う上で適した手段である。水が不在の場合には、十分な塩基が水素添加中に
反応剤および生成物の遷移状態を安定化させうるように存在しなければならない
。溶媒の非制限例には、メタノール、エタノール、ｎ‐プロパノール、イソプロ
パノール、Ｎ，Ｎ‐ジメチルホルムアミド、ｎ‐ブタノール、イソブタノール、
tert‐ブタノールおよびそれらの混合物がある；好ましい溶媒はエタノール、ｎ
‐プロパノール、Ｎ，Ｎ‐ジメチルホルムアミドおよびそれらの混合物からなる
群より選択される。溶媒が存在して、塩基が水溶液の形であるとき、水性塩基の
上記容量対上記溶媒の比率は約１：１０〜約１：１、好ましくは水性塩基の容量
対溶媒の比率は１：４である。水性塩基および溶媒は２相系を形成することが望
ましいが、必須ではない。As a suitable alternative, step (a) may be performed in the presence of a solvent other than water or in the absence of water. A suitable solvent and water mixture is also a suitable means for performing the hydrogenation process of the present invention. In the absence of water, sufficient base must be present to stabilize the reactants and product transition state during hydrogenation. Non-limiting examples of solvents include methanol, ethanol, n-propanol, isopropanol, N, N-dimethylformamide, n-butanol, isobutanol,
There are tert-butanol and mixtures thereof; preferred solvents are ethanol, n
-Propanol, N, N-dimethylformamide and mixtures thereof. When a solvent is present and the base is in the form of an aqueous solution, the ratio of the volume of the aqueous base to the solvent is from about 1:10 to about 1: 1, preferably the ratio of the volume of the aqueous base to the solvent is 1: 4. It is. Preferably, but not necessarily, the aqueous base and solvent form a two-phase system.

【００１８】 本発明のプロセスには、単離ステップとして、任意だが好ましいステップ（ｂ
）がある。典型的には、このステップでは触媒を除去するために反応液の濾過を
行う。加えて、このステップには中和ステップを伴ってもよいが、しかしながら
生成物は業者が望むように反応マトリックスから単離または除去することができ
る。In the process of the present invention, an optional but preferred step (b
). Typically, this step involves filtering the reaction to remove the catalyst. In addition, this step may involve a neutralization step, however, the product can be isolated or removed from the reaction matrix as desired by the supplier.

【００１９】 触媒の濾過が望まれるステップであるとき、架橋リガンドを含有した反応液は
濾過して触媒を除去し、粗製濾液を形成する。この粗製濾液を中和しても、ある
いはテトラアザ大環式リガンドを好ましくは水溶液から直接に抽出または結晶化
により単離してもよい。When filtration of the catalyst is the desired step, the reaction containing the bridging ligand is filtered to remove the catalyst and form a crude filtrate. The crude filtrate may be neutralized, or the tetraaza macrocyclic ligand may be isolated, preferably by direct extraction or crystallization from an aqueous solution.

【００２０】 ステップ（ａ）、（ｂ）およびそれ以外の任意ステップ、例えば結晶化ステッ
プ、溶媒乾燥ステップ、パージステップは、バッチプロセスまたは連続プロセス
、例えば連続フロープロセスに適宜合わせてよい。前記のように、本発明のプロ
セスは業者により必要および／または望ましいと思われる他の任意ステップを含
んでもよい。これらの任意ステップには、水素による触媒の前飽和、系の真空吸
引、触媒および溶媒の回収があるが、それらに限定されない。Steps (a), (b) and any other steps, such as a crystallization step, a solvent drying step, a purge step, may be adapted to a batch or continuous process, such as a continuous flow process. As noted above, the process of the present invention may include any other steps deemed necessary and / or desirable by those skilled in the art. These optional steps include, but are not limited to, pre-saturation of the catalyst with hydrogen, vacuuming the system, and recovering the catalyst and solvent.

【００２１】 好ましくは、本発明のプロセスにより形成されたリガンドは、後の、しかしな
がら任意のプロセスステップで、マンガン含有遷移金属触媒へ変換される。その
ブリーチ触媒は、中心マンガン原子と、本発明のプロセスにより形成された架橋
リガンドからなる。最終ブリーチ触媒は、１以上の他の適合性リガンド、特に塩
素原子を含んでもよい。好ましい触媒は漂白剤として適している。 以下は本発明のプロセスの非制限例である。[0021] Preferably, the ligand formed by the process of the present invention is converted to a manganese-containing transition metal catalyst in a later, but optional, process step. The bleach catalyst consists of a central manganese atom and a bridging ligand formed by the process of the present invention. The final bleach catalyst may contain one or more other compatible ligands, especially chlorine atoms. Preferred catalysts are suitable as bleaches. The following is a non-limiting example of the process of the present invention.

【００２２】５，１２‐ジエチル‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６．２〕ヘ
キサデカンの製造 壁厚のガラスオートクレーブスリーブに、下記式を有するビス四級システトラ
サイクル： 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2]
Xadecane production wall thickness glass autoclave sleeve with bis quaternary cis tetracycle having the formula:

【化１９】 （３．０ｇ、６．８mmol）およびＫ２ＣＯ３の１Ｍ水溶液（３０ｍｌ）を加える
。その溶液を攪拌して基質を溶解させ、２０％Ｐｄ（ＯＨ）２／炭素（０．７ｇ
、１．０mmol）を加える。ガラススリーブをロッキングオートクレーブに入れて
、６５℃で４時間にわたり１９００ｐｓｉｇ水素で水素添加する。反応液を冷却
し、溶液をガラスファイバー濾紙で濾過して、触媒を除去し、濾液を真空下で白
色固体物に濃縮する。その白色固体物を還流エタノールに懸濁し、未溶解無機塩
を濾取する。真空下で濾液を濃縮した後、得られた油状残渣を水性４Ｍ ＫＯＨ
（４ｍｌ）に溶解し、トルエン２５ｍｌずつで３回抽出する。トルエン抽出液を
合わせ、真空下で濃縮して、透明油状物として収率８１％で５，１２‐ジエチル
‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６．２〕ヘキサデカン（１．５
６ｇ）を得る。Embedded image (3.0 g, 6.8 mmol) and a 1 M aqueous solution of K 2 CO 3 (30 ml) are added. The solution was stirred to dissolve the substrate and 20% Pd (OH) 2 / carbon (0.7 g
, 1.0 mmol). The glass sleeve is placed in a rocking autoclave and hydrogenated at 65 ° C. with 1900 psig hydrogen for 4 hours. The reaction is cooled, the solution is filtered through glass fiber filter paper to remove the catalyst, and the filtrate is concentrated under vacuum to a white solid. The white solid is suspended in refluxing ethanol and undissolved inorganic salts are filtered off. After concentrating the filtrate under vacuum, the resulting oily residue was washed with aqueous 4M KOH
(4 ml), and extracted three times with 25 ml each of toluene. The toluene extracts were combined and concentrated in vacuo to afford a 81% yield of 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane as a clear oil (1. 5
6 g) are obtained.

【００２３】 以下は、マンガン遷移金属ブリーチ触媒へ変換する、本発明のプロセスの任意
だが好ましいステップの例である。ジクロロ５，１２‐ジエチル‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６
．２〕ヘキサデカンマンガンの製造 １００ｍｌ反応フラスコに、無水アセトニトリル（５０ｍｌ）および５，１２
‐ジエチル‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６．２〕ヘキサデカ
ン（１．４ｇ、５mmol）を入れる。得られた懸濁液を真空下で脱気してから、ア
ルゴンで再充填する。このプロセスを６回繰り返す。塩化マンガン(II)（０．５
９０ｇ、４．７mmol）を加え、反応液を３時間還流する。得られた溶液をガラス
ファイバー濾紙で濾過する。得られた濾液を減圧下４５℃で濃縮して、固体物を
得る。その固体物をトルエン（５０ｍｌ）に懸濁し、得られた暗色上澄を捨てる
。トルエン処理を５回繰り返す。得られた固体物を真空下で乾燥させて、ジクロ
ロ５，１２‐ジエチル‐１,５,８,１２‐テトラアザ‐ビシクロ〔６．６．２〕
ヘキサデカンマンガン（１．４８ｇ、収率７３％）を得る。The following are examples of optional but preferred steps of the process of the present invention that convert to a manganese transition metal bleach catalyst. Dichloro 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6
. 2] Preparation of manganese hexadecane In a 100 ml reaction flask, anhydrous acetonitrile (50 ml) and 5,12
-Diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane (1.4 g, 5 mmol). The resulting suspension is degassed under vacuum and then refilled with argon. This process is repeated six times. Manganese (II) chloride (0.5
90 g, 4.7 mmol) are added and the reaction is refluxed for 3 hours. The solution obtained is filtered through a glass fiber filter paper. The obtained filtrate is concentrated at 45 ° C. under reduced pressure to obtain a solid. The solid is suspended in toluene (50 ml) and the resulting dark supernatant is discarded. Repeat the toluene treatment 5 times. The solid obtained is dried under vacuum to give dichloro 5,12-diethyl-1,5,8,12-tetraaza-bicyclo [6.6.2]
Hexadecanemanganese (1.48 g, 73% yield) is obtained.

───────────────────────────────────────────────────── フロントページの続き (81)指定国 ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＣＹ， ＤＥ，ＤＫ，ＥＳ，ＦＩ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，Ｉ Ｔ，ＬＵ，ＭＣ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ ，ＣＦ，ＣＧ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＧＷ，ＭＬ， ＭＲ，ＮＥ，ＳＮ，ＴＤ，ＴＧ)，ＡＰ(ＧＨ，ＧＭ，Ｋ Ｅ，ＬＳ，ＭＷ，ＳＤ，ＳＬ，ＳＺ，ＴＺ，ＵＧ，ＺＷ )，ＥＡ(ＡＭ，ＡＺ，ＢＹ，ＫＧ，ＫＺ，ＭＤ，ＲＵ， ＴＪ，ＴＭ)，ＡＥ，ＡＬ，ＡＭ，ＡＴ，ＡＵ，ＡＺ， ＢＡ，ＢＢ，ＢＧ，ＢＲ，ＢＹ，ＣＡ，ＣＨ，ＣＮ，Ｃ Ｒ，ＣＵ，ＣＺ，ＤＥ，ＤＫ，ＤＭ，ＥＥ，ＥＳ，ＦＩ ，ＧＢ，ＧＤ，ＧＥ，ＧＨ，ＧＭ，ＨＲ，ＨＵ，ＩＤ， ＩＬ，ＩＮ，ＩＳ，ＪＰ，ＫＥ，ＫＧ，ＫＰ，ＫＲ，Ｋ Ｚ，ＬＣ，ＬＫ，ＬＲ，ＬＳ，ＬＴ，ＬＵ，ＬＶ，ＭＡ ，ＭＤ，ＭＧ，ＭＫ，ＭＮ，ＭＷ，ＭＸ，ＮＯ，ＮＺ， ＰＬ，ＰＴ，ＲＯ，ＲＵ，ＳＤ，ＳＥ，ＳＧ，ＳＩ，Ｓ Ｋ，ＳＬ，ＴＪ，ＴＭ，ＴＲ，ＴＴ，ＵＡ，ＵＧ，ＵＳ ，ＵＺ，ＶＮ，ＹＵ，ＺＡ，ＺＷ (71)出願人 ＯＮＥ ＰＲＯＣＴＥＲ ＆ ＧＡＮＢＬ Ｅ ＰＬＡＺＡ，ＣＩＮＣＩＮＮＡＴＩ， ＯＨＩＯ，ＵＮＩＴＥＤ ＳＴＡＴＥＳ ＯＦ ＡＭＥＲＩＣＡ (72)発明者 クリストファー、マーク、パーキンズ アメリカ合衆国オハイオ州、シンシナチ、 ファーンバンク、アベニュ、7230 Ｆターム(参考） 4C050 AA03 BB10 CC20 EE04 FF01 GG01 HH01 4H039 CA42 CB90 ──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Application Person ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Christopher, Mark, Perkins Cincinnati, Ohio, United States of America, Fernbank, Avenue, 7230 F10A FF FF FF GG 001 HH01 4H039 CA42 CB90

Claims (12)

【特許請求の範囲】[Claims] 【請求項１】 下記式を有するテトラアザ大環式リガンド： 【化１】 （上記式中各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２）ｘ ＣＯ２Ｍおよびそれらの混合物であるが、但しＲ単位が双方ともメチルであるこ
とはない；Ｍは水素または塩形成カチオンである；ｘは１〜６である；各インデ
ックスｎは独立して０〜３である）を製造するための方法であって、 ａ）下記式を有するテトラアザ大環式リガンド前駆体： 【化２】 （上記式中Ｘ−は電荷中性をもたらすアニオンである）を、少くとも８のｐＨで
、１ｐｐｍ以上の遷移金属水素添加触媒で水素添加して、テトラアザ大環式リガ
ンドを形成し；および ｂ）場合により、上記のリガンドを単離する； ステップからなる上記製造方法。1. A tetraaza macrocyclic ligand having the formula: (Wherein each R is independently C 1 -C 8 straight or branched alkyl, — (CH 2 ) x CO 2 M and mixtures thereof, provided that the R units are not both methyl M is hydrogen or a salt-forming cation; x is from 1 to 6; each index n is independently from 0 to 3), wherein: Cyclic ligand precursor: (Wherein X − is an anion providing charge neutrality) with at least 1 ppm of a transition metal hydrogenation catalyst at a pH of at least 8 to form a tetraaza macrocyclic ligand; and b. Optionally) isolating said ligand; said method comprising the steps of: 【請求項２】 遷移金属水素添加触媒が、白金、パラジウム、水酸化パラジウム、ロジウム、
ラネーニッケルおよびそれらの混合物からなる群より選択される、請求項１に記
載の方法。2. A transition metal hydrogenation catalyst comprising platinum, palladium, palladium hydroxide, rhodium,
The method of claim 1, wherein the method is selected from the group consisting of Raney nickel and mixtures thereof. 【請求項３】 ステップ（ａ）が４０〜１００℃の温度、少くとも１０のｐＨおよび溶媒の存
在下で行われ、その溶媒が水、Ｎ，Ｎ‐ジメチルホルムアミド、メタノール、エ
タノール、イソプロパノール、ｎ‐ブタノール、イソブタノール、tert‐ブタノ
ールおよびそれらの混合物からなる群より選択される、請求項１または２に記載
の方法。3. The step (a) is carried out at a temperature of from 40 to 100 ° C., at a pH of at least 10 and in the presence of a solvent, the solvent comprising water, N, N-dimethylformamide, methanol, ethanol, isopropanol, n The method according to claim 1 or 2, wherein the method is selected from the group consisting of -butanol, isobutanol, tert-butanol and mixtures thereof. 【請求項４】 前駆体が下記式を有している： 【化３】 上記式中ＲおよびＸは前記と同義である、請求項１〜３のいずれか一項に記載の
方法。4. The precursor has the following formula: The method according to any one of claims 1 to 3, wherein R and X have the same meanings as described above. 【請求項５】 各Ｒがエチルである、請求項１〜４のいずれか一項に記載の方法。5. The method according to claim 1, wherein each R is ethyl. 【請求項６】 １つのＲがメチルで、１つのＲがエチルである、請求項１〜５のいずれか一項
に記載の方法。6. The method according to claim 1, wherein one R is methyl and one R is ethyl. 【請求項７】 下記式を有するテトラアザ大環式リガンド： 【化４】 （上記式中一方のＲ単位はメチルで、他方のＲ単位はエチル、プロピル、ブチル
、ペンチル、ヘキシルおよびそれらの混合物からなる群より選択される）を製造
するための方法であって、 ａ）下記式を有するテトラアザ大環式リガンド前駆体： 【化５】 （上記式中Ｘ−は電荷中性をもたらすアニオンである）を、少くとも１０のｐＨ
で、１ｐｐｍ以上のパラジウム水素添加触媒で水素添加して、テトラアザ大環式
リガンドを形成し；および ｂ）場合により、上記のリガンドを単離する； ステップからなる上記製造方法。7. A tetraaza macrocyclic ligand having the formula: Wherein one R unit is methyl and the other R unit is selected from the group consisting of ethyl, propyl, butyl, pentyl, hexyl and mixtures thereof, comprising: a) Tetraaza macrocyclic ligand precursor having the formula: (Wherein X − is an anion providing charge neutrality) at a pH of at least 10.
Hydrogenating with 1 ppm or more of a palladium hydrogenation catalyst to form a tetraaza macrocyclic ligand; and b) optionally isolating the ligand. 【請求項８】 下記式を有するテトラアザ大環式リガンド： 【化６】 （上記式中各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２）ｘ ＣＯ２Ｍおよびそれらの混合物であるが、但しＲ単位が双方ともメチルであるこ
とはない；Ｍは水素または塩形成カチオンである；ｘは１〜６である；各インデ
ックスｎは独立して０〜３である）を製造するための方法であって、 ａ）下記式を有するテトラアザ大環式リガンド前駆体： 【化７】 （上記式中Ｘ−は電荷中性をもたらすアニオンである）を、０〜１００℃の温度
で、溶媒の存在下（その溶媒は水、メタノール、エタノール、Ｎ，Ｎ‐ジメチル
ホルムアミド、ｎ‐ブタノール、イソブタノール、tert‐ブタノールおよびそれ
らの混合物からなる群より選択される）、少くとも８のｐＨで、１ｐｐｍ以上の
パラジウム水素添加触媒（そのパラジウム触媒は担持パラジウム（０）、水酸化
パラジウムおよびそれらの混合物からなる群より選択される）で水素添加して、
テトラアザ大環式リガンドを形成し； ｂ）触媒を濾去して、粗製濾液を形成し；および ｃ）場合により、結晶化、抽出、蒸留または他の適切な手段により上記のリガ
ンドを単離する； ステップからなる上記製造方法。8. A tetraaza macrocyclic ligand having the formula: embedded image (Wherein each R is independently C 1 -C 8 straight or branched alkyl, — (CH 2 ) x CO 2 M and mixtures thereof, provided that the R units are not both methyl M is hydrogen or a salt-forming cation; x is from 1 to 6; each index n is independently from 0 to 3), wherein: Cyclic ligand precursor: (Wherein X − is an anion providing charge neutrality) at a temperature of 0 to 100 ° C. in the presence of a solvent (the solvent is water, methanol, ethanol, N, N-dimethylformamide, n-butanol). , Isobutanol, tert-butanol and mixtures thereof), at least at a pH of 8 and at least 1 ppm of a palladium hydrogenation catalyst, wherein the palladium catalyst is supported palladium (0), palladium hydroxide and their mixtures. Selected from the group consisting of mixtures of
Forming a tetraaza macrocyclic ligand; b) filtering off the catalyst to form a crude filtrate; and c) optionally isolating said ligand by crystallization, extraction, distillation or other suitable means. The above-described production method comprising the steps of: 【請求項９】 架橋テトラアザ大環式遷移金属触媒を形成するために、リガンドをマンガンで
処理するステップを更に含む、請求項８に記載の方法。9. The method of claim 8, further comprising treating the ligand with manganese to form a bridged tetraaza macrocyclic transition metal catalyst. 【請求項１０】 下記式を有するテトラアザ大環式リガンド： 【化８】 （上記式中Ｒ単位は、メチルおよびエチル、ジエチル、メチルおよびプロピル、
エチルおよびプロピル、メチルおよびブチル、エチルおよびブチル、およびそれ
らの混合物からなる群より選択されるＲ単位対である；Ｍは水素または塩形成カ
チオンである；ｘは１〜６である；各インデックスｎは独立して０〜３である）
を製造するための方法であって、 ａ）下記式を有するテトラアザ大環式リガンド前駆体： 【化９】 （上記式中Ｘ−は電荷中性をもたらすアニオンである）を、少くとも８のｐＨで
、１ｐｐｍ以上の遷移金属水素添加触媒で水素添加して、テトラアザ大環式リガ
ンドを形成し；および ｂ）場合により、上記のリガンドを単離する； ステップからなる上記製造方法。10. A tetraaza macrocyclic ligand having the formula: embedded image (In the above formula, R unit is methyl and ethyl, diethyl, methyl and propyl,
A pair of R units selected from the group consisting of ethyl and propyl, methyl and butyl, ethyl and butyl, and mixtures thereof; M is hydrogen or a salt-forming cation; x is 1-6; Is independently 0 to 3)
Comprising: a) a tetraaza macrocyclic ligand precursor having the formula: (Wherein X − is an anion providing charge neutrality) with at least 1 ppm of a transition metal hydrogenation catalyst at a pH of at least 8 to form a tetraaza macrocyclic ligand; and b. Optionally) isolating said ligand; said method comprising the steps of: 【請求項１１】 ａ）下記式を有する架橋リガンド： 【化１０】 （上記式中各Ｒは独立してＣ１‐Ｃ８直鎖または分岐アルキル、‐（ＣＨ２）ｘ ＣＯ２Ｍおよびそれらの混合物であるが、但しＲ単位が双方ともメチルまたはブ
チルであることはない；Ｍは水素または塩形成カチオンである；ｘは１〜６であ
る；各インデックスｎは独立して０〜３である）； ｂ）マンガン；および ｃ）場合により、１以上の適合性リガンド； からなる遷移金属触媒。11. a) A cross-linked ligand having the formula: Wherein each R is independently C 1 -C 8 straight or branched alkyl, — (CH 2 ) x CO 2 M and mixtures thereof, provided that both R units are methyl or butyl M is hydrogen or a salt-forming cation; x is 1-6; each index n is independently 0-3); b) manganese; and c) optionally one or more compatibility A transition metal catalyst comprising: a ligand; 【請求項１２】 下記式を有する： 【化１１】 請求項１１に記載の化合物。12. It has the following formula: A compound according to claim 11.
JP2000585243A 1998-11-30 1999-11-18 Method for producing cross-linked tetraaza macrocycles Withdrawn JP2002531457A (en)

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