JP2002531457A - Method of manufacturing a cross-linked tetra-aza macrocycles such - Google Patents

Method of manufacturing a cross-linked tetra-aza macrocycles such

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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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クリストファー、マーク、パーキンズ
ジョージ、ダグラス、ヒラー、ザ、セカンド
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ザ、プロクター、エンド、ギャンブル、カンパニー
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Priority to PCT/US1999/027316 priority patent/WO2000032601A2/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00Compounds containing elements of Groups 7 or 17 of the Periodic System
    • C07F13/005Compounds without a metal-carbon linkage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts 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
    • B01J31/1805Catalysts 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
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic 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
    • B01J31/182Cyclic 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08Bridged systems
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/96Water

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C ‐C 直鎖または分岐アルキル、‐(CH CO M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) Abstract: The present invention is contacted at a temperature of from about 40 to about 100 ° C., in an aqueous solution having a pH of at least about 10, in the presence of a palladium catalyst, diquaternary cis tetra cycles precursor with hydrogen by, crosslinked tetraaza macrocyclic ligand (each R is independently C 1 -C 8 linear or branched alkyl, having formulas (I) - a (CH 2) x CO 2 M and mixtures thereof; However that R units are both methyl; M is hydrogen or a salt forming cation; x is 1 to 6; process for producing each index n is 0-3 independently) on.

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。 The present invention relates to an improved process for the production of crosslinked tetraazacyclododecane macrocycle compound, the macrocyclic compounds are suitable as ligands useful in producing a transition metal complex. 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 provides a well suitable process for use in industrial and other commercial production of crosslinked macrocycles such as 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。 Tetraazacyclododecane macrocycles, such cyclam (cyclam) has have been manufactured in many ways, however, in particular transition metal catalysts, especially in the field of bleach catalyst, crosslinking tetraaza the wide application as a ligand has been found recently macrocycle, in particular bis-N- substituted tetraazacyclododecane macrocycles include, inter alia 5,12 dialkyl -1,5,8,12- tetraaza - is lack of information regarding the production of bicyclo [6.6.2] hexadecane acids .

【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。 [0003] WO98 / 39335A1 in "an improved process for the preparation of the cross-linking macro Po recycling class", easy to obtain high yields necessary for the industrial scale-up, to produce cross-linked large polycyclic ligand (cross-bridged macropolycyclic ligands) It discloses a reasonable operation for. 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。 However, the reduction ring cleavage step which results in bicyclo bridged ring formation utilizes a borohydride reducing agent. このタイプの還元剤は業者に制約を課すことがある。 This type of reducing agent is sometimes impose constraints on skilled in the art. 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。 For example, the need to decompose the amine / boron hydride complex post-processing, as well as the proper recovery and disposal of boron waste, increases the cost of the process. 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。 Moreover, if an excess of borohydride is needed, requiring neutralization with a generating use and a large amount of hydrogen gas of the acid thereto.

【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] Thus, can be applied to a continuous flow process or batch production, crosslinked large polycyclic ligands manufactured to order highly quantitative of, preferably with respect to catalytic processes, there is a need.

【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, in that it has been found surprisingly that bis N- substituted tetraazacyclododecane macrocycles such selected can be converted into crosslinking atmospheric polycyclic ligand by catalytic hydrogenation, meets the needs.

【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] The first aspect of the present invention relates to a process for producing a tetraaza macrocyclic ligand having the formula:

【化12】 [Of 12] (上記式中各Rは独立してC ‐C 直鎖または分岐アルキル、‐(CH CO M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: (Each R in the formula is independently a C 1 -C 8 linear or branched alkyl, - (CH 2) a x CO 2 M and mixtures thereof, preferably do not both R units are methyl ; M is hydrogen or a salt forming cation; x is 1 to 6; each index n is 0-3 independently); the process comprising: a) tetraaza macrocyclic ligand precursor having the formula :

【化13】 [Of 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。 The - (the formula X is an anion leading to charge neutrality), at a pH of at least 8, and hydrogenated at about 1ppm or more transition metal hydrogenation catalyst, to form a tetraaza macrocyclic ligand; and b) optionally, comprising the step of isolating said 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。 [0007] These and other objects, features and advantages upon reading the claims, which are the following detailed description and accompanying will become apparent to those skilled in the art. 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。 Wherein all percentages, ratios and proportions are by weight unless otherwise noted. すべての温度は、別記されないかぎり摂氏度(℃)である。 All temperatures are in degrees Celsius unless otherwise noted (° C.). 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。 All documents cited are, in relevant parts are 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 a catalytic hydrogenation of tetra-aza macrocycles compound having the formula:

【化14】 [Of 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: Covalent binding of the N-substituted quaternary ring nitrogen and bridged carbon in the are broken, cross-linked macrocyclic ligand having the formula:

【化15】 [Of 15] が得られる生成物となる。 The product is obtained.

【0009】 上記式中、各Rは独立してC ‐C 直鎖または分岐アルキル、‐(CH [0009] In the above formulas, each R is independently C 1 -C 8 linear or branched alkyl, - (CH 2) CO M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。 an x CO 2 M and mixtures thereof, preferably not be both R units are methyl; more preferably one R unit is methyl and the other R unit is ethyl, propyl, butyl, pentyl, hexyl and mixtures selected from the group consisting of those; of methyl / alkyl R units mixture, preferably at one R is methyl, the other R is ethyl or propyl. 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。 The most preferred ligands are in one R unit is methyl, comprising units other R unit is ethyl. 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。 Preferred ligands are macrocyclic ring each R unit is ethyl. 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。 M is hydrogen or a salt forming cation, sodium its non-limiting example, potassium, calcium, ammonium. Rが‐(CH CO Mであるとき、インデックスxは1〜 R is - when (CH 2) a x CO 2 M, the index x is 1
約6の値であり、好ましくはxは1である。 About 6 is a value, which is preferably x 1. インデックスnがマクロサイクル環の大きさを決める。 Index n determines the size of the macrocycle ring. インデックスnは0〜約3の値を有している。 Index n has from 0 to about 3 values. 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 a preferred macrocycle ring, as represented by the following general formula, at opposite set of n indices 1, the other set of n indices is 0:

【化16】 [Of 16] 上記式中Rは前記と同義である。 The formula R is as defined 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。 [0010] Preferred ligands according to the invention are methyl and ethyl, have diethyl, methyl and propyl, ethyl and propyl, methyl and butyl, ethyl and butyl, and R units to be selected from the group consisting of a mixture thereof there.

【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: [0011] The starting materials of the process of the present invention is a tetraaza macrocyclic ligand precursor, or quaternary cis tetra cycle such bis having the following formula:

【化17】 [Of 17] 上記式中Rおよびnは前記と同義である。 It said wherein R and n are as defined above. 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。 X is an anion which serves to provide electrical neutrality bis quaternary cis tetra cycle. 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、 Those skilled in the art relates to the term "electroneutrality" is "sufficient amount of anionic species which satisfies the molecular charge balance requirements", 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。 2,3 mixtures of such charged species may be used here, to be understood. 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。 X is preferably a unit negative charge, for example, halogen, tosylate, methylsulfate, and ethylsulfate. 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。 However, X is had divalent or more negative charges, for example, it may be a sulfate, in which case the skilled in the art requires only half the amount necessary when using a unit negative charge anion. 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。 X is preferably 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: [0012] Step (a) hydrogenated - reductive cleavage step (a), as shown by the following scheme becomes et torn open reduction by catalytic hydrogenation added:

【化18】 [Of 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。 In the cis - tetra cycle bis quaternary salt is converted to crosslinked tetraazacyclododecane 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。 [0013] Step (a) the catalyst is preferably carried out in the presence of a supported catalyst. 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) /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。 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. 好ましい触媒はPd(OH) /Cである。 A preferred catalyst is Pd (OH) 2 / C.
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。 Although the supported catalyst comprises from about 1 to about 50 wt% of a transition metal, however pure metal, i.e. palladium "carrier", i.e. may be used without the need for carbon. 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。 "Catalytic amount" of catalyst is enough in performing the reduction of step (a). 本発明の目的にとり、 Taken for the purposes of the present invention,
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。 The term catalytic amount is defined as "about 1ppm or 5 wt% transition metal catalyst". 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。 However, skill is due to the toxicity of the catalyst surface with the reaction products may be used a catalytic amount or more catalysts. 本発明のステップ(a)で用いられる触媒の量は、 The amount of catalyst used in step (a) of the present invention,
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、 Preferably about 10ppm or more catalysts contained about 5 to 50 wt% of a transition metal,
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。 Transition metal supported catalyst at more preferably about 100ppm or more, even more preferably about 0.1% by weight or more. 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 0.1 wt% of a transition metal supported catalyst (the catalyst can, for example, containing 10 wt% palladium on carbon) reaction solution containing the 0.0
1%遷移金属または100ppm遷移金属を存在させている。 And the presence of 1% transition metal or 100ppm transition metal.

【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 The amount of the hydrogen gas present in step (a) of the present invention may be fully saturated even the catalyst surface, preferably hydrogen pressure 200 psi, more preferably 400ps
i、最も好ましくは800psiから、約2000psi、更に好ましくは10 i, and most preferably from 800 psi, about 2000 psi, more preferably 10
00psiまでである。 00psi is up to.

【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℃、 [0015] The process of step (a), 20 ° C., preferably about 40 ° C., more preferably from about 60 ° C., about 100 ° C., preferably about 90 ° C., more preferably about 80 ° C.,
最も好ましくは約65℃までの温度で行える。 Most preferably performed at a temperature of 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 [0016] Step pH should (a) is performed, at least 8, preferably at least 10
、更に好ましくは少くとも約11である。 , About 11 with still more preferably at least. 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。 Preferably, the base used to adjust the pH is in the form of an aqueous solution. 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。 Preferred bases are potassium ,, carbonate, sodium carbonate, sodium hydroxide, is selected from the group consisting of potassium hydroxide and mixtures thereof. 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 Non-limiting examples, 1 a sufficient amount to adjust the pH to the required level
M(モル)水性塩基を用いれば、それでよい。 The use of M (mol) aqueous base, so good. 好都合な好ましい塩基は炭酸カリウムである。 Conveniently 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。 [0017] Suitable alternative, step (a) may be carried out in the absence of presence or water solvent other than water. 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。 Mixture of suitable solvents and water is also a suitable means in carrying out the hydrogenation process of the present invention. 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。 If water is absent, sufficient base should be present so as to be able to stabilize the transition state of the reactants and products during hydrogenation. 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、 Non-limiting examples of solvents include methanol, ethanol, n- propanol, isopropanol, N, N-dimethylformamide, n- butanol, isobutanol,
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 tert- butanol and mixtures thereof is; preferred solvents are ethanol, 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。 - propanol, N, is selected from the group consisting of N- dimethylformamide and mixtures thereof. 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。 The solvent is present, when the base is in the form of aqueous solutions, the volume to the ratio of the solvent of the aqueous base is about 1: 10 to about 1: 1, preferably capacitance versus the ratio of solvent in the aqueous base of 1: 4 it is. 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。 Aqueous base and solvent, it is desirable to form a two phase system, but not required.

【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 [0018] The process of the present invention, as isolated steps, but optional but preferred step (b
)がある。 ) There is. 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。 Typically, performing the filtration of the reaction mixture to remove the catalyst in this step. 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 addition, it may be accompanied by neutralization step This step, however product can be isolated or removed from the reaction matrix as skilled desires.

【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。 [0019] When a step of filtration of the catalyst is desired, the reaction solution containing a crosslinking ligand filtered to remove the catalyst, to form a crude filtrate. 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。 It is neutralized The crude filtrate, or tetraaza macrocyclic ligand preferably may be isolated by extraction or crystallization directly 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。 [0020] Step (a), (b) and other optional steps, such as crystallization step, solvent drying step, purge step, a batch or continuous process, for example, be combined as appropriate to a continuous flow process. 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。 As described above, the process of the present invention may include other optional steps deemed necessary and / or desirable by the art. 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。 These optional steps, before saturation of the catalyst with hydrogen, the vacuum suction of the system, there is a recovery of the catalyst and solvent, but is not limited thereto.

【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。 [0021] Preferably, the ligand that is formed by the process of the present invention, after the, however in any process step are converted into manganese-containing transition metal catalyst. 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。 Its bleach catalyst is a central manganese atom, comprising a crosslinked ligand formed by the process of the present invention. 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。 The final bleach catalysts, one or more other compatible ligand, may particularly include a chlorine atom. 好ましい触媒は漂白剤として適している。 Preferred catalysts are suitable as a bleaching agent. 以下は本発明のプロセスの非制限例である。 The following are non-limiting examples 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 [0022] 5,12-diethyl -1,5,8,12- tetraaza - bicyclo [6.6.2] f
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: A glass autoclave sleeve manufacturing wall thickness of hexadecane, bis quaternary cis tetra cycle having the following formula:

【化19】 [Of 19] (3.0g、6.8mmol)およびK CO の1M水溶液(30ml)を加える。 (3.0 g, 6.8 mmol) and K added 1M aqueous solution of 2 CO 3 (30ml). その溶液を攪拌して基質を溶解させ、20%Pd(OH) /炭素(0.7g The solution stirred to dissolve the substrate and the, 20% Pd (OH) 2 / carbon (0.7 g
、1.0mmol)を加える。 , Adding 1.0mmol). 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。 The glass sleeve placed in locking autoclave and hydrogenated at 1900psig hydrogen for 4 hours at 65 ° C.. 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。 The reaction was cooled, the solution was filtered through a glass fiber filter paper to remove the catalyst and the filtrate is concentrated to a white solid under vacuum. 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。 And suspending the white solid in refluxing ethanol, collected by filtration undissolved inorganic salts. 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 After concentrating the filtrate under vacuum and the resulting oily residue aqueous 4M KOH
(4ml)に溶解し、トルエン25mlずつで3回抽出する。 Dissolved in (4 ml), and extracted three times with portions of toluene 25 ml. 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 The combined toluene extracts were concentrated under vacuum, as a clear oil in 81% yield 5,12-diethyl -1,5,8,12- tetraaza - bicyclo [6.6.2] hexadecane (1. 5
6g)を得る。 Obtain 6g).

【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。 [0023] The following are converted to manganese transition metal bleach catalysts, examples of arbitrary but is preferably a step of the process of the present invention. 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 Dichloro 5,12-diethyl -1,5,8,12- tetraaza - bicyclo [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 The production 100ml reaction flask 2] hexadecane manganese, anhydrous acetonitrile (50ml) and 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。 - Diethyl -1,5,8,12- tetraaza - bicyclo [6.6.2] add hexadecane (1.4g, 5mmol). 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。 The resulting suspension was degassed under vacuum and refilled with argon. このプロセスを6回繰り返す。 This process is repeated six times. 塩化マンガン(II)(0.5 Manganese chloride (II) (0.5
90g、4.7mmol)を加え、反応液を3時間還流する。 90 g, 4.7 mmol) is added and the reaction refluxed for 3 hours. 得られた溶液をガラスファイバー濾紙で濾過する。 The resulting solution is filtered through a glass fiber filter paper. 得られた濾液を減圧下45℃で濃縮して、固体物を得る。 The resulting filtrate was concentrated under reduced pressure at 45 ° C., to obtain a solid. 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。 The solid was suspended in toluene (50 ml), discarding the dark supernatant obtained. トルエン処理を5回繰り返す。 Repeat the toluene treatment 5 times. 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〕 The resulting solid was dried under vacuum, dichloro 5,12-diethyl -1,5,8,12- tetraaza - bicyclo [6.6.2]
ヘキサデカンマンガン(1.48g、収率73%)を得る。 Hexadecane Manganese (1.48 g, 73% yield).

───────────────────────────────────────────────────── 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 ────────────────────────────────────────────────── ─── of the front page continued (81) designated States 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 , 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) application people ONE PROCTER & GANBL E PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) inventor Christopher, mark, Perkins United States, Ohio, Cincinnati, Fernbank, Abenyu, 7230 F-term (reference) 4C050 AA03 BB10 CC20 EE04 FF01 GG01 HH01 4H039 CA42 CB90

Claims (12)

    【特許請求の範囲】 [The claims]
  1. 【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】 1. A tetraaza macrocyclic ligand having the formula: ## STR1 ## (上記式中各Rは独立してC ‐C 直鎖または分岐アルキル、‐(CH CO M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】 (Each R in the formula is independently a C 1 -C 8 linear or branched alkyl, - (CH 2) is a x CO 2 M and mixtures thereof, with the proviso that R units are both methyl ; M is hydrogen or a salt forming cation; x is 1 to 6; a method for producing the index n is 0 to 3 independently), a) tetraaza size having the formula cyclic ligand precursor: ## STR2 ## (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。 The - (the formula X is an anion leading to charge neutrality), at a pH of at least 8, and hydrogenated at 1ppm or more transition metal hydrogenation catalyst, to form a tetraaza macrocyclic ligand; and b ) optionally, the ligand isolating; above manufacturing method comprising steps.
  2. 【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、 2. A transition metal hydrogenation catalyst, platinum, palladium, palladium hydroxide, rhodium,
    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。 It is selected from the group consisting of Raney nickel and mixtures thereof, The method of claim 1.
  3. 【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。 Wherein step (a) is 40 to 100 ° C. temperature, carried out in the presence of pH and solvent at least 10, the solvent is water, N, N- dimethylformamide, methanol, ethanol, isopropanol, n - butanol, isobutanol, tert- butanol and is selected from the group consisting of mixtures thereof, the method according to claim 1 or 2.
  4. 【請求項4】 前駆体が下記式を有している: 【化3】 4. A precursor has the formula: ## STR3 ## 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。 The formulas R and X are as defined above, the method according to any one of claims 1 to 3.
  5. 【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。 A wherein each R is ethyl, the method according to any one of claims 1-4.
  6. 【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。 In 6. One R is methyl, one R is ethyl, the method according to any one of claims 1 to 5.
  7. 【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】 7. tetraaza macrocyclic ligand having the formula: 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】 (In R units one in the above formula is a methyl, the other R unit ethyl, propyl, butyl, pentyl, selected from the group consisting of hexyl and mixtures thereof) A method for producing, a) tetraaza macrocyclic ligand precursor having the following formula: 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 (Wherein X - is an anion resulting in charge neutrality) a, pH of at least 10
    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。 In, was hydrogenated at 1ppm or more palladium hydrogenation catalyst, tetraaza macrocyclic ligand to form; a and b) if the above-mentioned ligand isolating; above manufacturing method comprising steps.
  8. 【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】 8. tetraaza macrocyclic ligand having the formula: 6] (上記式中各Rは独立してC ‐C 直鎖または分岐アルキル、‐(CH CO M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】 (Each R in the formula is independently a C 1 -C 8 linear or branched alkyl, - (CH 2) is a x CO 2 M and mixtures thereof, with the proviso that R units are both methyl ; M is hydrogen or a salt forming cation; x is 1 to 6; a method for producing the index n is 0 to 3 independently), a) tetraaza size having the formula cyclic ligand precursor: ## STR00007 ## (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、 (Wherein X - is an anion resulting in charge neutrality), and at a temperature of 0 to 100 ° C., the presence of a solvent (the solvent is water, methanol, ethanol, N, N-dimethylformamide, n- butanol , isobutanol, is selected from the group consisting of tert- butanol and mixtures thereof), at a pH of at least 8, 1 ppm or more of a palladium hydrogenation catalyst (the palladium catalyst is palladium (0), palladium hydroxide and their was hydrogenated at to) selected from the group consisting of,
    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。 Tetraaza to form a macrocyclic ligand; b) by filtering off the catalyst, the crude filtrate was formed; and optionally c), crystallization, extraction, isolating said ligand by distillation or other suitable means ; the manufacturing method comprising steps.
  9. 【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. A for forming a crosslinked tetraaza macrocyclic transition metal catalyst, further comprising the step of treating the ligand with manganese method of claim 8.
  10. 【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】 10. tetraaza macrocyclic ligand having the formula: 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、 (Above wherein R units are methyl and ethyl, diethyl, methyl and propyl,
    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) Ethyl and propyl, R units to be selected from the group consisting of methyl and butyl, ethyl and butyl, and mixtures thereof; M is hydrogen or a salt forming cation; x is 1 to 6; each index n is 0-3 independently)
    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】 A method for producing a tetraaza macrocyclic ligand precursor having a) the following formula: 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。 The - (the formula X is an anion leading to charge neutrality), at a pH of at least 8, and hydrogenated at 1ppm or more transition metal hydrogenation catalyst, to form a tetraaza macrocyclic ligand; and b ) optionally, the ligand isolating; above manufacturing method comprising steps.
  11. 【請求項11】 a)下記式を有する架橋リガンド: 【化10】 11. a) bridging ligands having the formula: 10] (上記式中各Rは独立してC ‐C 直鎖または分岐アルキル、‐(CH CO M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。 (Each R in the above formula independently C 1 -C 8 linear or branched alkyl, - (CH 2) is a x CO 2 M and mixtures thereof, provided that it R units is methyl or butyl both no; M is hydrogen or a salt forming cation; x is 1 to 6; each index n is 0-3 independently); b) manganese; and by c) if one or more compatible transition metal catalyst comprising; ligand.
  12. 【請求項12】 下記式を有する: 【化11】 12. having the formula: 11] 請求項11に記載の化合物。 A compound according to claim 11.
JP2000585243A 1998-11-30 1999-11-18 Method of manufacturing a cross-linked tetra-aza macrocycles such Withdrawn JP2002531457A (en)

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