TW200829331A

TW200829331A - Rhodium-tellurium intermetallic compound particle, method for producing the same, and use of the same

Info

Publication number: TW200829331A
Application number: TW096135322A
Authority: TW
Inventors: Atsushi Muramatsu; Hideyuki Takahashi; Hironobu Ohno; Kazunari Takahashi
Original assignee: Mitsubishi Chem Corp; Univ Tohoku
Priority date: 2006-09-25
Filing date: 2007-09-21
Publication date: 2008-07-16
Also published as: WO2008041534A1; CN101516504A

Abstract

For the purpose of efficiently producing a high-purity rhodium-tellurium intermetallic compound particle, a solution containing a rhodium salt, a tellurium salt and a complexing agent is brought into contact with a reducing agent and an organic compound containing a sulfur atom and/or a nitrogen atom is used as the complexing agent.

Description

200829331 九、發明說明：【發明所屬之技術領域】其：:;：：關於鍺-碲金屬間化合物粒子之製造方法及由 ;匕人碲金相化合物粒子，與使用祕-碲金屬間生：:：：之氧化觸媒，暨使用該氧化觸媒之氧化性加成生成物的製造方法。【先前技術】200829331 IX. Description of the invention: [Technical field to which the invention pertains] It::::: A method for producing ruthenium-iridium intermetallic compound particles; and a ruthenium-based metallographic compound particle, which is produced by using a secret-ruthenium metal: And: an oxidation catalyst, and a method for producing an oxidative addition product using the oxidation catalyst. [Prior Art]

，為進仃共扼二烯之氧化性酿氧基化反應的觸媒，工業主要使用PdTe系觸媒。 ’、 :此二相較於PdTe系觸媒’ RhTe系觸媒具有極高之選糸納碰若可使用，則由經濟性極優越之方面而言，RhTe =媒之開發將有極大意義。然而，晰⑽媒由於在反應中Rh會大量溶解於屬於溶媒的醋酸中，故活性於極紐日守間内便降低，因此迄今尚未到達工業化。方面作為製造合金粒子的一般技術，已知混合含有金^鹽之溶液與含有還原劑之溶液，此時使還原反應進 :丁而得到合金粒子的方法。具體而言，係採用如非專利文獻1所記載，於經加熱之還原溶媒中滴下金屬鹽溶液的方法L或如專利文獻1所記载，於經加熱之金屬鹽溶液中滴下延原劑溶液的方法等。然而，依此等方法係一邊將還原劑與^屬鹽進行混合·擴散，一邊進行還原反應，故金屬鹽之還原方式會發生差異，結果只能得到不均質的合金粒為改善此問題，並以提高還原反應速度，使混合•擴散 312XP/發明說明書(補件)/97-01/96135322 5 200829331 之影響減低化為目的，於專利文獻2中提案有將事先於金屬鹽溶液中混合了還原力較弱之第一還原劑的溶液，滴^ -至將含有具強還原力之第二還原劑的溶液進行加熱者中 v 的方法，但其效果並不充分。 Λ 另外，於非專敎獻2中，記載有❹乙二胺四醋酸 (EDTA)作為錯合劑，依中性的條件與還原劑接觸但此方法中由於使經錯合的Rh鹽析出’故即使於其後進行還原馨操作，仍難以合成金屬間化合物。 ’、 (非專利文獻 l)J0urnal of the American Chewed Society, 83, 4916, 1962 (非專利文獻2)第96回觸媒討論會預稿集，3E12、3El3. (專利文獻1)日本專利特開昭61-12802號公報 (專利文獻2)美國專利4294608號公報【發明内容】 (發明所欲解決之問題） • 本發明係有鑑於上述實情而提出者。亦即，本發明之目的在於提供可有效率地製造高純度之姥一碎金屬間化合物粒子的方法，與藉由該方法所製造之錄一碑金屬間化合物 Γ子以及長1供一種使錢-碲金屬間化合物粒子載持於載 $上而成之氧化觸媒，其絲以溶出姥、&經時性劣化較本發明亚提供使㈣氧化觸媒之氧化性加成 V 製造方法。 (解決問題之手段）本發明者等人有鑑於上述問題而潛心研究，結果發現， 312ΧΡ/發明說明書(補件)/97_〇1/96135322 200829331 措由使用含有硫原子及/或氮原子之有機化合物，，並使含有姥鹽及蹄鹽以及錯合劑之溶液與還原^ 觸，則可有效率地製造高純度之鍺_碲金接子，又，在將所得之錄-蹄金屬間化合物子_ 而作成氧化觸媒時，屬於活性種之_以溶出载== 化少，遂完成本發明。 ' 为亦即’本發明之要旨在於一種姥— =有姥及碑之金屬間化合物粒子，其特^ 仫為6〜16nm，铑與碲之原子比為3 圍第H)。巧2 3. 4(申睛專利範於此，鍺與碲之原子比較佳為3 : 2、3 : 4或丨：！之一者（申請專利範圍第2項）。本發明之其他要旨在於—種氧化觸媒，其特徵為係將本舍明之姥-碲金屬間化合物粒子載持於载體申專利範圍第3項）。 mat明 ;b $ ^ ^氧化觸媒較佳為if氧基化反應用觸媒 (申請專利範圍第4項）。 ,本發明之其他要旨在於—種姥—碲金屬間化合物粒子之衣k方法/、餐彳政為，至少具備將含有鍺鹽及碲鹽以及錯合劑之溶液與還原劑接觸的步驟，上述錯合劑為含有硫原子及/或U子之有機化合物（申請專利範圍第5項）。於此較么係使上述之鍺鹽及碲鹽以及錯合劑溶解於鹼性水溶液後，、再與還原劑接觸（申請專利範圍第6項）。另外上述錄鹽較佳為氯化鍺（申請專利範圍第7項）。 312XP/發明說明書(補件)/97·〇1/96135322 ? 200829331 另外，上述碲鹽較佳為從由碲酸及其鹽類以及亞碲酸及其鹽類所組成群選出（申請專利範圍第8項）。另外，本發明之其他要旨在於一種铑—碲金屬間化合物粒子’其特徵4，係藉由上述之製造方法所獲得利範圍第9項）。In order to promote the oxidative ethoxylation reaction of decadiene, the industry mainly uses PdTe-based catalyst. ‘, : The two phases are more selective than the PdTe-based catalysts. RhTe-based catalysts can be used. In terms of economic superiority, the development of RhTe = media will be of great significance. However, since the Rh (10) medium is largely dissolved in the acetic acid belonging to the solvent in the reaction, the activity is reduced in the active phase, so that it has not yet reached industrialization. As a general technique for producing alloy particles, it is known to mix a solution containing a gold salt and a solution containing a reducing agent, and at this time, a reduction reaction is carried out to obtain alloy particles. Specifically, a method L of dropping a metal salt solution into a heated reducing solvent as described in Non-Patent Document 1 or a method of dropping a solution of a prolonged agent in a heated metal salt solution as described in Patent Document 1 is employed. Method, etc. However, according to these methods, the reduction reaction is carried out while mixing and diffusing the reducing agent and the genus salt, so that the reduction method of the metal salt is different, and as a result, only the alloy particles having the unevenness can be obtained to improve the problem. In order to increase the reduction reaction rate and reduce the influence of the mixing/diffusion 312XP/invention specification (supplement)/97-01/96135322 5 200829331, it is proposed in Patent Document 2 that the metal salt solution is previously mixed and reduced. The solution of the first reducing agent having a weaker force is dropped to a method of heating the solution containing the second reducing agent having a strong reducing power, but the effect is not sufficient. Λ In addition, in the non-specialized 2, EDTA is described as a wronging agent, which is contacted with a reducing agent according to neutral conditions, but in this method, the mismatched Rh salt is precipitated. Even after the reduction operation, it is difficult to synthesize an intermetallic compound. ' (Non-Patent Document 1) J0urnal of the American Chewed Society, 83, 4916, 1962 (Non-Patent Document 2) Pre-collection of the 96th Catalyst Workshop, 3E12, 3El3. (Patent Document 1) Japanese Patent Laid-Open Japanese Patent Publication No. 4294608 (Patent Document 2) SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances. That is, the object of the present invention is to provide a method for efficiently producing high-purity ruthenium-intermetallic compound particles, and a scorpion intermetallic compound scorpion manufactured by the method and a long one for one kind of money - an oxidizing catalyst in which the ruthenium intermetallic compound particles are supported on a carrier, and the ruthenium is added to the oxidized addition V of the (4) oxidation catalyst. (Means for Solving the Problem) The inventors of the present invention have intensively studied in view of the above problems, and as a result, found that 312 ΧΡ / invention specification (supplement) / 97_〇1/96135322 200829331 measures the use of a sulfur atom and/or a nitrogen atom. The organic compound, and the solution containing the cerium salt and the hoof salt and the complexing agent, can be efficiently produced to produce a high-purity ruthenium ruthenium metal bond, and the obtained hoof-homometallic compound When the oxidized catalyst is used as the oxidizing catalyst, it is classified as the active species. 'Yes, i.e., the present invention is intended to be an intermetallic compound particle having a ruthenium and a ruthenium, and its specific 仫 is 6 to 16 nm, and the atomic ratio of ruthenium to osmium is 3 Å. Qiao 2 3. 4 (Shenzhen patents are here, the atom of 锗 and 碲 is better than 3: 2, 3: 4 or 丨:! (applicable to the scope of patent application 2). Other aspects of the invention are intended to An oxidizing catalyst characterized in that the ruthenium-iridium intermetallic compound particles of the present invention are carried on the carrier patent claim 3 (3). Mat Ming; b $ ^ ^ Oxidation catalyst is preferably a catalyst for the ifoxylation reaction (article 4 of the patent application). The other method of the present invention is to provide a method for contacting a solution containing a cerium salt and a cerium salt and a complexing agent with a reducing agent, at least the coating method of the cerium-cerium intermetallic compound particles. The mixture is an organic compound containing a sulfur atom and/or a U group (application patent item 5). In this case, the above-mentioned cerium salt and cerium salt and the complexing agent are dissolved in an aqueous alkali solution, and then contacted with a reducing agent (Patent Patent No. 6). Further, the above-mentioned salt is preferably ruthenium chloride (item 7 of the patent application). 312XP/Invention Manual (Supplement)/97·〇1/96135322 ? 200829331 In addition, the above-mentioned cerium salt is preferably selected from the group consisting of citric acid and its salts, and linoleic acid and its salts (application patent scope) 8 items). Further, other aspects of the present invention are directed to a ruthenium-iridium intermetallic compound particle 'the feature 4 which is obtained by the above-described production method, item 9).

另外’本發明之其他要旨在於―種氧化觸媒，其特徵為’係使上述之铑-碲金相化合物粒子載持成（申請專利範圍第1〇項）。而另外’本發明之其他要旨在於—種氧化性加成生成物之 =造方法4特徵為，在上述之氧化觸似分子狀氧的存下，使乳親核劑氧化性地加成至稀煙或 (申請專利範圍第11項）。化口物 (發明效果）根據本發明’可藉由較簡單之方法，有效率度之铑-碲金屬間化合物粒子。、。间砘另二’使所得之铑-碲金屬間化合物粒子载持於，化觸媒’係具有姥不易溶出、經時性【實施方式】以炎點。以下詳細說明本發明，但本發明並不限定於以在其要旨之範圍内可進行各種變化而實施。兄月 [1.銘-碌金屬間化合物粒子之製造方法] 本發明之鍺-碲金屬間化合物粒子之夢造當簡稱為「本發明之製造方法」），係具有使下適碲鹽以及錯合劑之溶液與還原劑接觸二人十老鹽及沙日合劑為含 312XP/發明說明書(補件)/97-01/96135322 8 200829331 有硫原子及/或氮原子之有機化合物。、本么明中，藉由控制金屬鹽及錯合劑以及還原劑的種類、還原反應時之pH，則可控制金屬鹽之還原屬度，合成出均質的奈米金屬間化合物。 [1 -1·铑鹽] 作為本發明之製造方法所使用之鍺鹽，可舉例如無機化合物（铑之氧化物、硝酸鹽、硫酸鹽等）、鹵化物（铑之氯化物等）、有機酸鹽（铑之醋酸鹽等）、錯合鹽（铑之氨 (瞻ine)錯合物等）、有機金屬化合物⑽之乙醯丙明錯合物等）等。又’亦可將黯屬本身溶解於反應溶液中而使其中’、作為鍺鹽，較佳係含有鍺之無機化合物、鍺之齒化物、或含有鍺之有機金屬化合物，更具體使用鍺之氯化物。馬尚且’錢鹽可單獨使用任-種，亦可依任意組合及比例將2種以上組合使用。 [1 -2·碲鹽] 作為本發明之製造方法所使用之碲鹽，可舉例如盖機化 a物（碲之氧化物、械料酸及其鹽類、亞碲酸及盆之 :類等广齒化物(碲之氣化物、漠化物等)、有機碲化合反^本Λ二碑化物等）等。又’亦可將蹄金屬本身溶解於反應〉各液中而使用。 ^中二作為碲鹽’較佳係含有叙無機化合物、碌之齒物、3有碲之有機_化合物’更佳為含有碲之無機氧化 312ΧΡ/發明說明書(補件)/97-01/96135322 9 200829331 物或碲之氯化物。其鹽類暨亞碲酸及其鹽作為碲鹽，尤其係以從由碲酸及顯所組成群選出之化合物為最佳。尚且，碲鹽可單獨使用任將2種以上組合使用。 [1 - 3 ·錯合劑] 種，亦可依任意組合及比例本發明之製造方法中，錯合劑為極重要之因子。友本發明之製造方法的特徵在於，使用含有硫原子及/或氮原子之有機化合物作為錯合劑。作為含有硫原子或氮原子之錯合劑的例子，可舉例如有機酸、磷化合物、肟類、醯胺類、胺類、醇類等。作為有機酸之具體例，可舉例如以下列舉之化合物。 D-2-胺基-3-酼基-3-曱基丁酸（D - 2-Amino - 3-Mercapto-3 ie1:hylbutanoic acid)(青黴胺（penicillamine):分子式 CsHnOAS)、 _ 亞胺基二醋酸（Iminodiacetic acid)(簡稱 IDA : C4Hr〇4N)、 (N - 環己基）亞胺基二醋酸 (N~(Cyclohexyl) iminodiacetic acid)(分子式：Further, the other aspect of the present invention is directed to an oxidation catalyst which is characterized in that the above-mentioned ruthenium-iridium metallographic compound particles are supported (claim No. 1 of the patent application). Further, the other method of the present invention is directed to an oxidative addition product, which is characterized in that, in the presence of the above-mentioned oxidative contact molecular oxygen, the milk nucleophile is oxidatively added to the rare Smoke or (application for patent scope 11). The chemical substance (the effect of the invention) According to the present invention, the ruthenium-iridium intermetallic compound particles can be efficiently obtained by a simple method. ,. The second ’ 使所得所得碲碲碲碲碲碲碲碲碲 , 碲 , , 碲。。。。。。。。。。。。。。。。。。。。。。 The present invention will be described in detail below, but the present invention is not limited thereto, and various modifications can be made without departing from the spirit and scope of the invention. The method of producing the 铭-碌 intermetallic compound particles of the present invention is abbreviated as "the manufacturing method of the present invention". The solution of the mixture and the reducing agent are contacted with the two-person aging salt and the sand-day mixture is an organic compound having a sulfur atom and/or a nitrogen atom in the 312XP/invention specification (supplement)/97-01/96135322 8 200829331. In the present invention, by controlling the metal salt, the type of the complexing agent and the reducing agent, and the pH at the time of the reduction reaction, the reducing degree of the metal salt can be controlled to synthesize a homogeneous nano-metal compound. [1 -1·铑 salt] The onium salt used in the production method of the present invention may, for example, be an inorganic compound (such as an oxide of cerium, a nitrate or a sulfate), a halide (such as a chloride of cerium), or an organic compound. An acid salt (such as an acetate of hydrazine), a mixed salt (such as an ammonia complex of hydrazine), an acetylamine complex of an organometallic compound (10), and the like. Further, it is also possible to dissolve the genus itself in the reaction solution to make it, as a cerium salt, preferably an inorganic compound containing cerium, a dentate of a cerium, or an organometallic compound containing cerium, more specifically using cerium chloride. Compound. Ma Shanghe's money can be used alone or in combination of two or more kinds in any combination and in any ratio. [1 -2·碲 salt] The onium salt used in the production method of the present invention may, for example, be a capped a substance (an oxide of lanthanum, a mechanical acid and a salt thereof, a phthalic acid, and a pot: Such as the wide-toothed compound (the gasification of bismuth, desertification, etc.), the organic bismuth compound, the anti-Ben Λ 碑碑、, etc.). Further, the hoof metal itself may be dissolved in the reaction liquid to be used. ^中二 as a bismuth salt 'better' contains an inorganic compound, a dentate, a ruthenium-organic compound _ ' 更无机无机无机无机无机发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明发明9 200829331 Chloride of matter or bismuth. The salts and the perindic acid and salts thereof are preferred as the onium salts, especially those selected from the group consisting of decanoic acid and succinic acid. In addition, the onium salt may be used alone or in combination of two or more. [1 - 3 · Wrong agent] The species may be in any combination and ratio. In the production method of the present invention, the complexing agent is a very important factor. The manufacturing method of the present invention is characterized in that an organic compound containing a sulfur atom and/or a nitrogen atom is used as a blocking agent. Examples of the complexing agent containing a sulfur atom or a nitrogen atom include organic acids, phosphorus compounds, hydrazines, guanamines, amines, and alcohols. Specific examples of the organic acid include the compounds listed below. D-2-Amino-3-mercapto-3-mercaptobutyric acid (D-2-Amino-3-Mercapto-3 ie1:hylbutanoic acid) (penicillamine: molecular formula CsHnOAS), _imino group Iminodiacetic acid (IDA: C4Hr〇4N), (N-(Cyclohexyl) iminodiacetic acid) (Molecular formula:

Ci〇Hi7〇4N) ^ 氮基三醋酸（Nitrilotriacetic acid)(簡稱NTA:分子式 C6H9〇6N)、 N-（2-四氫哌喃基曱基）亞胺基二醋酸 (N-(2-TetrahydropyranyImethy1)iminodiacetic acid) (分子式CuHLN)、 312XP/發明說明書(補件)/97·01/96135322 10 200829331 N-(2-羥基乙基）伸乙基二氮基-Ν，Ν’，Ν’ -三醋酸 (N-(2-Hydroxyethyl)ethylenedinitrilo-N，Ν’，Ν’ -tr . iacetic acid)(簡稱 HEDTA :分子式 CioHuOD、伸乙基二氮基四醋酸（Ethylenedinitrilotetraacetic acid)(簡稱 EDTA :分子式 GLN2)、 DL-（曱基伸乙基）二氮基四醋酸（DL -（Methylethylene) dinitrilotetraacetic acid)(簡稱 PDTA :分子式 CllHl8〇8N2)、 ⑩反-1，2-環己烯二氮基四醋酸（trans-1，2-Cyclohexylene dinitrilotetraacetic acid)(簡稱 CDTA :分子式 C14H22O8N2)、伸乙基雙（氧基伸乙基氮基）四醋酸 (Ethylenebis(oxyethylenenitrilo)tetraacetic acid) (簡稱 EGTA ··分子式、二伸乙基三氮基四醋酸 • (Diethylenetrinitrilotetraacetic acid)(簡稱 DTPA : 分子式 C14H23O1DN3)、三伸乙基四氮基六醋酸 (Triethylenetetranitrilohexaacetic acid)(簡稱 TTHA :分子式 CuHsoOuNO、 . 6-曱基吼〇定 _2-缓酸（6-Methlpyridine-2-carboxy 1 ic ^ acid)(分子式 d〇2N)、 N -（2-吼啶基曱基）亞胺基二醋酸 (N-（2-Pyridylmethyl)iminodiacetic acid)(分子式 312XP/發明說明書(補件)/97-01/96135322 11 200829331 C10H12O4N2)、式Z-SCH2CO2H所示之（取代硫基）醋酸（（substituted • thio)acetic acid)(上述式中，z表示曱基、乙基、丙基、、丁基、1-曱基丙基、戊基、己基等之碳數1〜30的烷基； 2-丙烯基（卩1*(^-2-61^1)、3-丁烯基（6111:-3-61^1)、4-戊烯基（Pent-4-enyl)等之碳數2〜30之烯基；苄基等之碳數 6〜30之芳基。）、 DL-巯基丁二酸（DL-Mercaptobutanedioic acid)(硫基蘋鲁果酸（thiomalic acid):分子式 C4H6O4S)、 (伸乙基二硫基）二醋酸（（Ethylenedithio)diacetic acid)(分子式 C6Hi〇〇4S2)、氧基雙（伸乙基硫基醋酸）（Oxybis(ethylenethioacetic acid))(分子式 C8Hu〇5S2)、硫基雙（伸乙基硫基醋酸）（Thiobis(ethylenethioacetic acid))(分子式 C8Hn〇4S3)、 0 魏基甲基硫基丁二酸（Carboxymethylthiobutanedioic acid)(分子式 CeEUOeS)、 2, 2- 雙（羥基曱基）-3- Μ 基丙醇 (2,2-Bis(hydroxymethyl)-3-mercaptopropanol)(單硫基季戊四醇（monothiopentaerythtitol):分子式 . C5H12O3S)、硫基水揚酸（Thiosalicylic acid)(簡稱TS:分子式 C^HsChS) 〇作為磷化合物之具體例，可舉例如3-(二苯基膦基）苯 312XP/發明說明書(補件)/97-01/96135322 12 200829331 石黃酸 (3-(Diphenylphosphino)benzenesulfonic acid) (3- 磺酸基三苯基膦 . (3-sulfotriphenylphosphine):分子式 C18H15O3SP)等。作為肟類之具體例，可舉例如丁 -2, 3-二酮二肟Ci〇Hi7〇4N) ^ Nitrilotriacetic acid (NTA: molecular formula C6H9〇6N), N-(2-tetrahydropyranyl) imidodiacetic acid (N-(2-TetrahydropyranyImethy1) Iminodiacetic acid) (CuHLN), 312XP/invention specification (supplement)/97·01/96135322 10 200829331 N-(2-hydroxyethyl)-extended ethyldiazepine-anthracene, Ν', Ν'-three Acetic acid (N-(2-Hydroxyethyl)ethylenedinitrilo-N, Ν', Ν'-tr. iacetic acid) (HEDTA for short: molecular formula CioHuOD, Ethylenedinitrilotetraacetic acid (EDTA: molecular formula GLN2) , DL-(Methylethylene) dinitrilotetraacetic acid (PDTA: molecular formula CllHl8〇8N2), 10 trans-1,2-cyclohexyldiazide tetraacetic acid (trans -1,2-Cyclohexylene dinitrilotetraacetic acid) (CDTA: molecular formula C14H22O8N2), Ethylenebis (oxyethylenenitrilo) tetraacetic acid (referred to as EGTA · · molecular formula, di-ethyl Triazatetraacetic acid • (Diethylenetrini Trilotetraacetic acid) (referred to as DTPA: molecular formula C14H23O1DN3), Triethylenetetranitrilohexaacetic acid (TTHA: molecular formula CuHsoOuNO, . 6-mercaptopurine _2-acidic acid (6-Methlpyridine-2) -carboxy 1 ic ^ acid) (N-(2-Pyridylmethyl)iminodiacetic acid) (Molecular Formula 312XP/Invention Manual (Repair) )/97-01/96135322 11 200829331 C10H12O4N2), (substituted thio)acetic acid represented by the formula Z-SCH2CO2H (in the above formula, z represents a thiol group, an ethyl group, a propyl group, An alkyl group having 1 to 30 carbon atoms such as butyl, 1-mercaptopropyl, pentyl or hexyl; 2-propenyl (卩1*(^-2-61^1), 3-butenyl ( 6111:-3-61^1), 4-pentenyl (Pent-4-enyl) or the like having 2 to 30 carbon atoms; benzyl group or the like having 6 to 30 carbon atoms. ), DL-Mercaptobutanedioic acid (thiomalic acid: molecular formula C4H6O4S), (Ethylenedithio) diacetic acid (molecular formula C6Hi) 〇〇4S2), Oxybis (ethylenethioacetic acid) (Molecular Formula C8Hu〇5S2), Thiobis (ethylenethioacetic acid) (Molecular Formula) C8Hn〇4S3), 0 Carboxymethylthiobutanedioic acid (CeEUOeS), 2,2-bis(hydroxyindenyl)-3-mercaptopropanol (2,2-Bis(hydroxymethyl)-3 -mercaptopropanol) (monothiopentaerythtitol: molecular formula. C5H12O3S), Thiosalicylic acid (TS: molecular formula C^HsChS) 〇 As a specific example of the phosphorus compound, for example, 3-(II) Phenylphosphino)benzene 312XP/Invention Manual (supplement)/97-01/96135322 12 200829331 3-(Diphenylphosphino)benzenesulfonic acid (3-sulfotriphenylphosphine) : Molecular formula C18H15O3SP), etc.Specific examples of the anthraquinone include, for example, butyl-2,3-dione dioxime

V (Butane-2, 3-diondioxime)(二曱基乙二蔣 (dimethylglyoxime):分子式 C4H8O2N2)、1，2-二苯基乙烧 -1，2- 二將（1，2-Diphenylethane-1，2-dione dioxime)(M^*a-¥*:^(a-benzildioxiine):* ⑩子式C—2N2)等。醯胺類之具體例可舉例如以下化合物。硫基碳酸胺（111丨0031^31111(16)(硫基尿素（1：1^01^68):分子式 CH4N2S)、單硫基碳醯胺（Monothiooxamide)(分子式GfhONzS)、 N-N’ -雙（2-羥基乙基）單硫基氧基醯胺 (N, Ν’ -Bis(2-hydroxyethyl)monothiooxamide)(分子式 • C6H12O3N2S)、 N-N’ _雙（3_羥基丙基）單硫基氧基醯胺 (N，Ν’ -Bis(3-hydroxypropy1)monothiooxamide)(分子式 C8H16O3N2S)、 N-N’ _雙（4-經基丁基）單硫基氧基醯胺 . (1^，^-618(4-1^(11"〇又71)11士71)111〇11〇1:111〇〇又31111(16)(分子式 C10H20O3N2S) ' N-N’ -雙（5-羥基戊基）單硫基氧基醯胺 (N，Ν’ -Bis(5-hydroxypentyl)monothiooxamide)(分子 312XP/發明說明書(補件)/97-01/96135322 13 200829331 式 CuI^Os-S)、 N-Ν’ -雙（2-磺酸基乙基）二硫基氧基醯胺 .(Ν，Ν’ -Bis(2-sulfoethyl)dithiooxamide)(分子式 C6H12O6N2S4) 〇作為胺類之具體例，可舉例如以下之化合物。甲基胺（倾61：1^1311^116)(分子式（：115?0、乙基胺（Ethylamine)(分子式 C2H7N)、丙基胺（Propylamine)(分子式 C3H9N)、 _ 丁基胺（Butylamine)(分子式 C4H11N)、戊基胺（Pentylamine)(分子式 CsHuN)、己基胺（Hexylamine)(分子式 CeHisN)、異丁基胺（Isobutylamine)(分子式 C4H11N)、 2-胺基乙醇（2-Aminoethanol)(乙醇胺（ethanolamine): 分子式C2H7ON)、乙二胺（Ethylenediamine)(分子式 C2IM2)、 φ 三亞曱基二胺（Trimethylenediamine)(分子式 C3Hi〇N2)、四乙二胺（Tetraethylenediamine)(分子式 C4H12N2)、五亞甲基二胺（Pentamethylenediamine)(分子式〇ϋ)、 1，3-二胺基-2-丙醇（1，3-Diamino-2-propanol )(2-經基 • 三亞曱基二胺（2-hydroxytrimethylenediamine):分子式 .C3H10ON2) > 氧基雙（2 -乙基胺）（0xybis( 2-ethyl amine)) (1，7-二氮雜 -4-側氧基庚烧（17-Diaza-4-oxaheptane):分子式 312XP/發明說明書(補件)/97-01/96135322 14 200829331 C4H12ON2)、伸乙基雙（氧基-2_乙基胺）（Ethy 1 enebis(oxy-2-ethy 1 amine)) 0,10- 二氮雜 -4, 7- 二侧氧基癸烷 (1，10-diaza-4, 7-dioxadecane):分子式 C6H16O2N2)、硫基雙（2-乙基胺）（Thi〇bis(2-ethylamine))(l，7-二氮雜-4-嗟庚烧（l，7-diaza-4-thiaheptane):分子式 C4H12N2S)、 1，2, 3-三胺基丙烧（1，2, 3-Triaminopropane)分子式 • CH)、參（胺基曱基）甲烧（Tr is (ami nomethyl) met hane)(分子式 C4H13N3)、二曱基胺（Dimethylamine)(分子式 C2H7N)、 1，4, 三氮雜庚烧（1，4, 7-Triazaheptane)(分子式 C4H13N3) 〇作為醇類之具體例，可舉例如1，3-二羥基-4-(2-吡啶 _ 基偶氮）苯（1，3-dihydroxy-4-(2_pyridylazo)benzene) (簡稱PAR :分子式CnH9〇2N3)。其中，作為錯合劑，較佳為有機酸或醇類，具體而言，較佳為以下所列舉之化合物。氧基雙（伸乙基硫基醋酸）（〇xybis(ethylenethioacetic • acid))(分子式 CsHhOA)、 .N—(2—羥基乙基）伸乙基二氮基-N，N，，N，-三醋酸 (N-（2-Hydroxyethyl)ethylenedinitrilo-N，Ν，，N，-tr iacetic acid)(簡稱 HEDTA :組成式 Ci〇Hi8〇7N2)、 312xp/發明說明書(補件)/97-01/96135322 15 200829331 伸乙基二氮基四醋酸（Ethylenedinitrilotetraacetic acid)(簡稱 EDTA :組成式 CbH—)、 , 3-(二苯基膦基）笨磺酸(3-(Diphenylphosphino)benzenesulfonic acid)(3_ 磺酸基三苯基膦 (3-sulfotriphenylphosphine) ··分子式 CisHi5〇3SP)、 DL-魏基丁二酸（DL-Mercaptobutanedioic acid)(硫基蘋果酸（thiomalic acid):組成式 CdHeChS)、硫基水楊酸（Thiosal icy 1 ic acid)(簡稱TS _·組成式 • CMO2S) ' 1，3- 二羥基 -4-(2- 吡啶基偶氮）苯 (1，3-dihydroxy-4-（2-pyridylazo)benzene)(簡稱 PAR ·· 組成式 C11H9O2N3)。其中，作為錯合劑，更佳為伸乙基二氮基四醋酸 (Ethylenedinitrilotetraacetic acid)(簡稱 EDTA:組成式 Ci〇Hi6〇8N2)、硫基水揚酸（Thiosal icy 1 ic acid)(簡稱 ⑩TS ·組成式C7H6O2S)、1，3-二經基-4-(2-σ比咬基偶氮）苯 (1，3-(111^(11：〇父7-4-（2-07]：1(171&2〇)56112 6116)(簡稱？八民：組成式 CnH9〇2N3)。特佳為硫基水揚酸（Thiosalicylic acid)(簡稱TS:組成式 C7H6O2S)、1，二經基_4-(2-吼咬基偶氮）苯 • (1，3-dihydroxy-4-(2-pyridylazo)benzene)(簡稱 PAR : ，組成式 CnH9〇2N3)。尚且，上述例示之各種錯合劑，可單獨使用任一種，亦可依任意組合及比例將2種以上組合使用。 312XP/發明說明書(補件 y97-〇l/96135322 16 200829331 另外，視需要亦可使用以τ列舉之第二錯合劍。尤其是在使用碲酸作為碲鹽時，最好使用第二錯合劑。作為第二錯合劑，可舉例如具有«及/或經基，並可溶於水之錯合劑。作為具體例，可舉例如#檬酸、丙二酸、頻果酸、琥轴酸、酒石酸、順丁烯二酸、酞酸、酸性胺基酸、中性胺基酸、鹼性脖其、^缺#田基&專。其中’較佳為檸檬酸、 /酉石I、頻果酸，最佳為檸檬酸。 :且丄上述例示之第二錯合劑’可單獨使用任一種，亦可依任意組合及比例將2種以上組合使用。 Π-4·金屬鹽溶液] 、容ΐ:::!造方法中’係使用將錢鹽及碲鹽以及錯合劑成之溶液(以下稱為「金屬鹽溶液」），而進仃後述之還原反應。益f媒之種類’若為可解決本發明問題而發揮功效者，則 :任:=如通常使用水或有機溶媒。作子，可舉例如甲醇、乙醇等之醇類。水其二=媒，由容易控制PH之觀點而言，較佳為水，特佳為使用蒸餾水。 q 尚且’溶媒可單獨使用任一叮分/立將2種以上組合使用。亦可依任思組合及比例藉由於上述溶媒中混合鍺商碲臨谁耔扭入& 梵孤碲鹽及錯合劑，使铑鹽及 ?意進仃錯合，使鍺鹽及碲鹽溶媒中，γ π 1 金屬錯合體的狀態溶解於 /合琛甲，則可得到金屬鹽溶液。尚且，本發明之製造方法 I稭由遇原劑進行還原反 πχρ/@Η_^(補件)/97彻613迎 17 200829331 以及錯合劑完全溶解於金溶液。V (Butane-2, 3-diondioxime) (dimethylglyoxime: molecular formula C4H8O2N2), 1,2-diphenylethene-1,2-di(1,2-Diphenylethane-1, 2-dione dioxime) (M^*a-¥*:^(a-benzildioxiine): * 10 subform C-2N2) and the like. Specific examples of the guanamines include the following compounds. Sulfurylamine carbonate (111丨0031^31111(16) (thiourea urea (1:1^01^68): molecular formula CH4N2S), monothiooxamide (molecular formula GfhONzS), N-N' - N, Ν'-Bis(2-hydroxyethyl)monothiooxamide (Molecular Formula • C6H12O3N2S), N-N' _bis(3_hydroxypropyl)monosulfide N,Ν'-Bis(3-hydroxypropy1)monothiooxamide (Molecular Formula C8H16O3N2S), N-N'-bis(4-carbylbutyl)monothiooxydecylamine. (1^, ^-618(4-1^(11"〇71)11士71)111〇11〇1:111〇〇31111(16)(Molecular Formula C10H20O3N2S) 'N-N'-Bis(5-Hydroxypentyl) ) N, Ν'-Bis (5-hydroxypentyl) monothiooxamide (Molecule 312XP / invention specification (supplement) / 97-01/96135322 13 200829331 Formula CuI^Os-S), N- Ν'-Bis(2-sulfoethyl)dithiooxamide (Molecular Formula C6H12O6N2S4) 〇 As a specific example of the amine, for example The following compounds: methylamine (pour 61:1^1311^116) (molecular formula (:115?0, ethyl (Ethylamine) (Molecular Formula C2H7N), Propylamine (Molecular Formula C3H9N), Butylamine (Molecular Formula C4H11N), Pentylamine (CsHuN), Hexylamine (CiHisN) ), Isobutylamine (Molecular Formula C4H11N), 2-Aminoethanol (ethanolamine: Molecular Formula C2H7ON), Ethylenediamine (Molecular Formula C2IM2), φ Triterpenoid II Trimethylenediamine (Molecular Formula C3Hi〇N2), Tetraethylenediamine (Molecular Formula C4H12N2), Pentamethylenediamine (Molecular Formula), 1,3-Diamino-2-propanol (1,3-Diamino-2-propanol) (2-hydroxytrimethylenediamine: molecular formula. C3H10ON2) > Oxy-bis(2-ethylamine) (0xybis(2-ethyl) Amine)) (17-Diaza-4-oxaheptane): Molecular Formula 312XP/Invention Manual (Supplement)/97-01/96135322 14 200829331 C4H12ON2), Extension Ethyl bis(oxy-2-ethethylamine) (Ethy 1 enebis (oxy-2-ethy 1 am) Ine)) 0,10-diaza-4,7-dioxadecane (1,10-diaza-4, 7-dioxadecane): molecular formula C6H16O2N2), thiobis(2-ethylamine) Thi〇bis(2-ethylamine)) (l,7-diaza-4-thiaheptane: molecular formula C4H12N2S), 1,2,3-triaminopropane (1,2, 3-Triaminopropane) Molecular Formula • CH), Tr is (ami nomethyl) met hane (Molecular Formula C4H13N3), Dimethylamine (Molecular Formula C2H7N), 1,4, 1,4,7-Triazaheptane (Molecular Formula C4H13N3) 〇 As a specific example of the alcohol, for example, 1,3-dihydroxy-4-(2-pyridine-ylazo) Benzene (1,3-dihydroxy-4-(2_pyridylazo)benzene) (abbreviated as PAR: molecular formula CnH9〇2N3). Among them, as the complexing agent, an organic acid or an alcohol is preferable, and specifically, the compounds listed below are preferable. Oxy bis (ethylenethioacetic acid) (molecular formula CsHhOA), .N-(2-hydroxyethyl) extended ethyldiazide-N,N,,N,- N-(2-Hydroxyethyl)ethylenedinitrilo-N, hydrazine, N,-tr iacetic acid (HEDTA: composition formula Ci〇Hi8〇7N2), 312xp/invention specification (supplement)/97-01/ 96135322 15 200829331 Ethylenedinitrilotetraacetic acid (EDTA: composition formula CbH-), 3-(Diphenylphosphino)benzenesulfonic acid (3-sulfonate) 3-sulfotriphenylphosphine · · molecular formula CisHi5 〇 3SP), DL-Mercaptobutanedioic acid (thiomalic acid: composition CdHeChS), thiosalicylic acid (Thiosal icy 1 ic acid) (TS _·composed formula • CMO2S) '1,3-dihydroxy-4-(2-pyridylazo)benzene (1,3-dihydroxy-4-(2-pyridylazo) Benzene) (abbreviated as PAR · · composition C11H9O2N3). Among them, as a complexing agent, Ethylenedinitrilotetraacetic acid (EDTA: composition formula Ci〇Hi6〇8N2) and Thiosal icy 1 ic acid (referred to as 10TS · Composition C7H6O2S), 1,3-dipyridyl-4-(2-σ ratio azo azo)benzene (1,3-(111^(11:〇父7-4-(2-07]:1) (171&2〇)56112 6116) (referred to as? Bamin: composition formula CnH9〇2N3). Particularly good is Thiosalicylic acid (TS: composition formula C7H6O2S), 1, dipyridyl _4 -(2-dihydroxy-4-(2-pyridylazo)benzene) (abbreviated as PAR: , composition formula CnH9〇2N3). Further, the various exemplified agents described above may be Any one of them may be used alone or in combination of two or more types in any combination and ratio. 312XP/Invention Manual (Repair y97-〇l/96135322 16 200829331 In addition, a second wrong sword listed in τ may be used as needed. In particular, when tannic acid is used as the onium salt, it is preferred to use a second crosslinking agent. As the second crosslinking agent, for example, a compound having a « and/or a trans group and being soluble in water can be used. Specific examples include, for example, citric acid, malonic acid, frequency acid, succinic acid, tartaric acid, maleic acid, citric acid, acidic amino acid, neutral amino acid, basic neck, and Lack #田基&Special. Among them, 'preferably citric acid, / vermiculite I, frequency fruit acid, preferably citric acid. : and the second wrong agent exemplified above can be used alone or in combination. Two or more types can be used in combination according to any combination and ratio. Π-4·Metal salt solution], 容ΐ:::! In the method of making 'use a solution of money salt and strontium salt and a wrong agent (hereinafter referred to as " The metal salt solution "), and the reduction reaction described later is carried out. If the type of the agent is used to solve the problem of the present invention, then: =: = If water or an organic solvent is usually used, for example, For example, alcohols such as methanol and ethanol. Water = media, from the viewpoint of easy pH control, water is preferred, and distilled water is particularly preferred. q Also, the solvent can be used alone or in any of the two. It can be used in combination with the above. It can also be used according to the combination and proportion of the above-mentioned solvents. Mp; van Gogh salt and the wrong agent, so that the strontium salt and the 意仃仃 , , , , 碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲碲Further, in the production method of the present invention, the straw is reduced by the original agent, anti-π χ ρ / @ Η _ ^ (supplement) / 97 613 ying 17 200829331, and the complexing agent is completely dissolved in the gold solution.

應時，重要的是使鍺鹽及碲鹽鹽溶液中，成為無析出的均勻、隹ΐΐΐ以上要點，則使各金屬鹽（鍺鹽及碲鹽）和錯合劑二：解此合的方法並無特別限制。可將各金屬鹽和錯別溶解於溶媒後料以混合，亦可將金屬鹽及錯八浏先混合後再溶解於溶媒中。 σ 二而I 了防止金屬鹽溶液的析出，最好適當地選擇相In the case of the strontium salt and the cerium salt solution, it is important to make the metal salt (the cerium salt and the cerium salt) and the complexing agent two: There are no special restrictions. Each of the metal salts and the impurities may be dissolved in a solvent to be mixed, or the metal salt and the mixed salt may be mixed and dissolved in the solvent. σ II and I prevent the precipitation of the metal salt solution, preferably the phase is selected appropriately

上於溶媒之金屬鹽(铑鹽及碲鹽)及錯合劑的濃度、與混合•溶解時之溫度。亦Ρ將至屬鹽，谷液中之各金屬鹽（鍺鹽及碲鹽）及錯合劑的濃度，分別設為各金屬鹽(鍺鹽及碲鹽)及錯合劑之飽和洛解度以下的濃度。飽和溶解度係因各金屬鹽及錯合劑的種類和溶媒種類、溶解時之溫度等而異，可配合其而選擇各金屬鹽（铑鹽及碲鹽）及錯合劑的濃度。一般而言，相對於金屬鹽溶液之各金屬鹽（铑鹽及碲鹽） #的，度，係以金屬重量換算計’不論何者均通常為0.001 重量％以上、較佳0.005重量％以上、更佳〇〇1重量％以上，又通常為10重量％以下、較佳5重量％以下、更佳2重量％以下的範圍。另外，金屬鹽（铑鹽及碲鹽）中之各金屬原子（铑及碲）之έ有里的比例，係設為與目標之鍺_碲金屬間化合物之組成幾乎一致的各金屬原子進料比例。相對於金屬鹽（铑鹽及碲鹽）所具有之金屬原子（铑及碲）之錯合劑的使用量比例，可為配位於金屬之化學計算混合 312ΧΡ/發明說明書(補件)/97-01/96135322 18 200829331 比（stoichiometric mixture ratio)以上，但錯合劑之比例若過高，則因溶解度的關係，結果使金屬濃度變低，而 - 有以一次操作可載持的金屬量變少的情形，且於經濟方面 • 不佳。一般而言，通常為化學計算混合比之1· 0倍以上，又通常為10倍以下、較佳5倍以下、更佳2倍以下、特佳1 · 5倍以下的範圍。尚且，在不妨礙後述之還原反應的範圍内，金屬鹽溶液係除了上述之铑鹽、碲鹽、錯合劑及溶媒之外，亦可含有其他成分。作為其他成分之例子，可舉例如具有铑及碲以外之金屬原子的金屬鹽等。又，此等可單獨使用任一種，亦可依任意組合及比例將2種以上組合使用。 [1 -5·還原反應] 本發明之製造方法係具有將含有铑鹽及碲鹽以及還原劑之溶液（金屬鹽溶液），與還原劑接觸而進行還原反應的步驟。， £ 鲁一本發明之製造方法所使用之還原劑，若為可溶於金屬鹽 /谷液之溶媒，則其種類並無限制。作為還原狀具體例，可舉例如料之氮化合物、氣化蝴納等之硼化合物、甲駿等之_、蟻酸及其鹽等之羧酸類、曱醇等之醇類等。其中，作為還原劑，較佳為氫化爛鈉、肼。 - 尚且’上述例示之還原劑，。了早獨使用任一種，亦可依任思組合及比例將2種以上組合使用。作為运原劑之使用量，較伟後係可將上述金屬鹽溶液中所 312XP/發明說明書(補件)/97-〇1/96135322 200829331 含有的全部金屬錯合物予以充分還原為金屬的量。一般而言’相對於1當量金屬，通常可為i倍當量以上，若考慮到還原反應的效率，較佳為12當量以上、更佳 1.5倍當量以上、更佳2倍當量以上。又，若考慮到未反應物的後處理等，作為上限，通常為5〇〇倍當量以下、較佳100倍當量以下、更佳40倍當量以下。尚且’已㈣使用肼作為還原劑時’因為由肼所進行之运原反應係因所還原之金屬鹽種類和pH等條件而使還原反應有所差異，無法料之還原#量特定為—定，故於本發明中，設為每1莫耳肼為2當量。使金屬鹽溶液錢原”難觸的方法並無㈣。通常係於上述金屬鹽溶液中加入還原劑而混合，進行還原反應。 :可於至屬鹽’合液中直接加入還原劑而混合，但為屬！溶液之混合·溶解變得容易，故可預先將屬鹽溶液中並混合。劑溶液）加入至金血：：’：為溶媒’若為可將還原劑溶解者，則其種類並 ;:2錄単獨使用一種溶媒，亦可依任意組合及比將2種以上溶媒組合使用。溶媒相同的溶媒。吊使用與金屬鹽溶液之還原劑溶液中之還原量，亦無特別限制。在將^=f和遇原劑溶液的使用的情況，可、翁將逖原一洛液加入至金屬鹽溶液中劑之量滿足上述範圍屬“液中之金屬的還原 312XP/發明說明書(補件)/97-01/96135322 20 200829331 還原反應時的溫度，通常為55t:以上、較佳7〇。〇以上， :’通常為沸點以下、較佳9(rc以下、更佳8(rc以下的乾圍。若還原反應時之溫度過高，則由於還原反應快速地 =行，故有目標之金屬間化合物以外之物生成的情形；另一方面，若溫度過低，則還原力過弱而有無法得到目標之金f間化合物的情形ϋ下記載中，將上述規定的溫度範圍稱為「規定溫度範圍」。 Θ且使退原反應開始的順序，可舉例如以下二種手法，可使用任一種步驟。 •在即使加入還原劑而還原反應亦不進行之程度的低溫度 (未滿上述規定還原溫度範圍的溫度。通常為常溫以下、較佳1(TC以下、更佳5aC)下，於金屬鹽溶液中加入還原劑（還原劑溶液）並混合，其後升溫至使可充分使還原反應進行之溫度（上述規定溫度範圍内之溫度）的手法。 •預先將金屬鹽溶液加熱至使金屬鹽之還原反應充分進行馨之溫度（上述規定溫度範圍内之溫度），於此狀態下加入還原劑而使還原反應開始的手法。另外，於還原反應時，最好將反應液（於金屬鹽溶液中加入了還原劑的液）調整為驗性。具體而言，最好將反應液之pH設為通常1〇以上、較佳12以上、更佳13以上。若反應液之pH過低（亦即，鹼性過弱），則有無法形成Rh 錯合物的情形。調整反應液pH的手法並無限制，通常使用pjj調整劑。作為pH調整劑，若為不與金屬鹽中之金屬（铑或蹄）進 312XP/發明說明書(補件)/97-01/96135322 21 200829331 行配位、或不阻礙錯合配位程度的化合物，狀金屬#合㈣成般之低貝J具種類並盔限制。作為PH調整劑，可兴… .^ .卜了牛例如鹽酸、硝酸、硫酸、氨水、化鈉。，、中較仫為鹽酸、硝酸、氫氧The concentration of the metal salt (onium salt and sulfonium salt) and the complexing agent on the solvent, and the temperature at the time of mixing and dissolution. Also, the concentration of each metal salt (salt salt and strontium salt) and the wrong agent in the salt, the liquid solution is set to be equal to or less than the saturation degree of each metal salt (antimony salt and barium salt) and the wrong agent. concentration. The saturation solubility varies depending on the type of the metal salt and the complexing agent, the type of the solvent, the temperature at the time of dissolution, and the like, and the concentration of each of the metal salts (onium salt and onium salt) and the complexing agent can be selected. In general, the degree of each metal salt (onium salt and sulfonium salt) of the metal salt solution is generally 0.001% by weight or more, preferably 0.005% by weight or more, based on the weight of the metal. The amount is preferably 1% by weight or more, and is usually 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less. In addition, the ratio of each of the metal atoms (铑 and 碲) in the metal salt (yttrium salt and yttrium salt) is set to be a metal atom feed which is almost identical to the composition of the target 锗_碲 intermetallic compound. proportion. The ratio of the amount of the metal atom (铑 and 碲) to the metal salt (铑 and 碲) may be the stoichiometric mixture of the metal 312ΧΡ/invention specification (supplement)/97-01 /96135322 18 200829331 (stoichiometric mixture ratio) or more, if the ratio of the cross-linking agent is too high, the metal concentration is lowered due to the solubility relationship, and the amount of metal that can be carried in one operation is reduced. And in terms of economy, it is not good. In general, the stoichiometric mixing ratio is usually 1.0 or more, and usually 10 or less, preferably 5 or less, more preferably 2 or less, and particularly preferably 1.5 or less. Further, the metal salt solution may contain other components in addition to the above-mentioned onium salt, onium salt, a complexing agent and a solvent, within a range not inhibiting the reduction reaction described later. As an example of other components, for example, a metal salt having a metal atom other than ruthenium and osmium may be mentioned. Further, these may be used alone or in combination of two or more kinds in any combination and in any ratio. [1 - 5·Reduction reaction] The production method of the present invention has a step of bringing a solution (metal salt solution) containing a cerium salt and a cerium salt and a reducing agent into contact with a reducing agent to carry out a reduction reaction. , Lu Reducing agent used in the manufacturing method of the invention is not limited as long as it is a solvent soluble in metal salt/gluten. Specific examples of the reduction form include a nitrogen compound such as a nitrogen compound, a boron compound such as vaporized sulfonate, a carboxylic acid such as formic acid or a salt thereof, an alcohol such as decyl alcohol, or the like. Among them, as the reducing agent, sodium hydride and hydrazine are preferred. - Still the 'reducing agent exemplified above. If you use one of them in advance, you can use them in combination of two or more types depending on the combination and ratio. As the amount of the carrier, the amount of all metal complexes contained in the above metal salt solution 312XP/invention specification (supplement)/97-〇1/96135322 200829331 can be sufficiently reduced to the amount of metal. . In general, it is usually i times equivalent or more with respect to 1 equivalent of the metal, and is preferably 12 equivalents or more, more preferably 1.5 equivalents or more, still more preferably 2 equivalents or more, in consideration of the efficiency of the reduction reaction. In addition, in consideration of the post-treatment of the unreacted material, the upper limit is usually 5 〇〇 equivalent or less, preferably 100 equivalents or less, more preferably 40 equivalents or less. Also, 'have (4) when using hydrazine as a reducing agent' because the original reaction carried out by hydrazine differs depending on the type of metal salt to be reduced and the pH, and the reduction reaction cannot be expected. Therefore, in the present invention, it is assumed to be 2 equivalents per 1 mole. There is no method for making the metal salt solution "different". (IV) Usually, a reducing agent is added to the above metal salt solution and mixed to carry out a reduction reaction. The reducing agent may be directly added to the mixture of the genus salt and mixed. However, it is easy to mix and dissolve the solution, so it is possible to mix and mix the salt solution in advance. The agent solution is added to the golden blood:: ': is the solvent'. If the reducing agent can be dissolved, the type And: 2 recording the use of a single solvent, can also be used in any combination and ratio of two or more solvents. The same solvent as the solvent. The amount of reduction in the reducing agent solution using the metal salt solution is not particularly limited. In the case of using ^=f and the solution of the original agent, the amount of the agent can be added to the metal salt solution, and the amount of the agent in the above range is "reduction of the metal in the liquid 312XP / invention manual ( Supplement) /97-01/96135322 20 200829331 The temperature at the time of the reduction reaction is usually 55t: or more, preferably 7〇. 〇 above, : 'usually below the boiling point, preferably 9 (rc or less, better 8 (dry circumference of rc or less. If the temperature during the reduction reaction is too high, the reduction reaction is fast = row, so there is a target metal On the other hand, if the temperature is too low, the reducing power is too weak and the target compound of gold f cannot be obtained. In the following description, the above-mentioned predetermined temperature range is referred to as "regulation. In the order of the start of the de-reaction reaction, for example, the following two methods can be used, and any one of the steps can be used. • A low temperature (not exceeding the above-mentioned regulations) to the extent that the reduction reaction is not carried out even if a reducing agent is added. The temperature in the range of the reduction temperature is usually below normal temperature, preferably 1 (TC or less, more preferably 5 aC), and a reducing agent (reducing agent solution) is added to the metal salt solution and mixed, and then the temperature is raised until the reduction reaction can be sufficiently performed. The temperature at which the temperature is carried out (the temperature within the above specified temperature range). • The metal salt solution is heated in advance to allow the reduction reaction of the metal salt to be sufficiently carried out at a temperature (in the above specified temperature range). Temperature), a method of adding a reducing agent to start the reduction reaction in this state. Further, in the case of the reduction reaction, it is preferred to adjust the reaction liquid (liquid in which the reducing agent is added to the metal salt solution) to be inspective. In other words, it is preferable that the pH of the reaction liquid is usually 1 or more, preferably 12 or more, and more preferably 13 or more. If the pH of the reaction liquid is too low (that is, the alkalinity is too weak), Rh may not be formed. The condition of the reaction solution is not limited, and the pjj modifier is usually used. As a pH adjuster, if it is not metal with a metal salt (铑 or hoof), the 312XP/invention specification (supplement)/97 -01/96135322 21 200829331 Compounds that coordinate or do not hinder the degree of mismatch, the metal #合(四) is generally low-shelled and has a helmet limitation. As a pH adjuster, it can be... Cattle such as hydrochloric acid, nitric acid, sulfuric acid, ammonia water, sodium, etc., in the middle of the hydrazine is hydrochloric acid, nitric acid, hydrogen and oxygen

尚且，pH調整劑可單獨使用及比例將2種以上組合使用。任一種，亦可依任意組合使用pH調整劑調整pH的步反應前，在保持金屬鹽不析出调整為上述規定範圍内。具體一者均可。驟並無限制。可於進行還原的狀態下，將反應液的pH 而言，可舉例以下步驟，任 •將姥鹽、碲鹽及錯合劑分別溶解於溶媒中後，在將此 t混合而調製金屬鹽溶液前，藉由邱調整劑個別地調整各溶液的pH。 •在=製成含有㈣、碲鹽及錯合劑之金屬鹽溶液後，在供於還原反應前，藉由pH調整劑調整此金屬鹽溶液的♦ •調製金屬鹽溶液，在還原反應不進行的溫度條件（未滿上述規定溫度範圍之溫度條件）下加入還原劑後，在將反應液加熱至還原反應進行之溫度條件（上述規定溫度範圍内之溫度條件）前，藉由pH調整劑調整此反應液的pH。尚且’ pH調整劑所進行的pH調整，可一次進行，亦可分為二次以上進行。 [1 -6·後處理] 藉§上述之還原反應，可得到铑—碲金屬間化合物粒 312ΧΡ/發明說明書(補件)/97-〇 1/96135322 22 200829331 子。所得之铑-碲金屬間化合物粒子可直接使用，亦可視需要進行分離、洗淨、乾燥、熱處理等之後處理。作為將所得之姥-碲金屬間化合物粒子自反應液分離的方法並播限& ’可採用例如使用遽紙或遽布的過濃法、，分離、沉澱分離(傾析法等)等。其中，一般係採用過濾、法。此等手法可單獨使用任一種，亦可依任意組合將2 種以上組合使用。在將所刀離之鍺—碲金屬間化合物粒子進行洗淨時的溶劑（洗淨溶劑）若非與铑-碲金屬間化合物粒 :反應者、或對錢-碲金屬間化合物粒子之二途)造成不良影響者，則無限定，通常可舉例如與1 可用之溶媒為同種的溶媒。又’洗淨溶劑早獨使用任__種，亦可依任意組合及比例並用。燥ΐ將二Γ士或洗淨)後之姥'蹄金屬間化合物粒子進行乾 "4之屋力亚無限制’可為常Μ、減壓（或真空）下進行乾燥。附近（Μ或多少的加減Μ)之條件作為乾燥方式，可舉例如供爐等之靜置式轉蒸發器般之旋轉式乾燥、固定床氣:、動= 二，乾燥機等之喷霧乾燥、覆帶式爐加=乾專之移送型乾燥等，可使用任—帛 urnace) =式，選定係視處理量等而決定，从方法，最好係使氣體流通而進行乾焊。種作為乾燥時所流通的氣體，•㈣，由_ 312XP/^H^W(M#)/97-〇l/96135322 23 200829331 =，：常使用空氣、氮等。又，於進行鍺，金屬間化 :物粒子之風處理時，於乾燥時可於所流通之氣體中加入虱。化===在於乾燥後不進行氫處理而將錢-蹄金屬間化5物拉子使用於所需用途上體，由經濟性觀點而言，較佳為气。又/：^土幻月性氣 2用任種，村錄意組合及比㈣2似上組合使 t ，速地進行乾燥的觀點而言’較佳係於過埶水瘵乳之流通下進行乾燥。乾燥時之溫度亦無特別限制 ==劑一下進行乾燥二= ::二乾燥或洗乎洛诏之愁氣壓提高的加埶乾焊.^r... ffl 燥。於加熱乾燥的情況，乾鮮又係使用加熱乾。。以下的範圍。在所⑼t /通常為40 c以上、綱、兄，由防卜叁#丨机之轧肢為過熱水蒸氣以外的情况由防止心、劇之突彿的_以 # 淨溶劑之下的溫度進行處理。^之公媒或洗在對乾煉後之鍺—碲金屬 _ ^ 作為熱處理之方式，可〜丨^ /物拉子切熱處理時’ 菽發哭等之牛丨j如烘爐等之靜置式、窯或旋轉 …、知寻之％轉式、固定、、古 ^ 式等，可採用任一種。机木、覆帶式爐等之移送乾燥方式之選定係視處理量等而決定，不論使用任何- 312XP/發明說明書(補件)机_6135322 ^ 200829331 種乾燥方法，最好係一邊使氣體流通一邊進行乾燥。产作為流通之氣體，較佳為不含氧之氣體。具體可舉例如氮、氬、氦等之惰性氣體；氫等。此等氣體可單獨使用任一種’亦可依任意組合及比例將2種以上組合使用。其中’較佳係將氮或氫單獨或作為混合物而使用。熱處理之溫度的下限，通常為100°C以上、較佳丨5(rc 以上、更佳200°C以上、再更佳3〇〇°C以上。熱處理之溫度的上限，通常可為鍺—碲金屬間化合物粒子之熔點以下，若過高，則铑—碲金屬間化合物粒子因燒結而雙大，金屬表面積降低，故將所得之铑-碲金屬間化 ^物粒子使用於觸媒用途時之觸媒活性會降低。因此，由提升觸媒活性之觀點而言，熱處理溫度之上限通常為議 °c以下、較佳60(rc以下、更佳5〇(rc以下。 [2 ·錢-碲金屬間化合物粒子] 藉本發明之製造方法所得之铑—碲金屬間化合物粒子 (以下稱為「本發明之铑—碲金屬間化合物粒子」或簡稱為本考X月之粒子」），通常為高純度之由姥及碲所形成的金屬間化合物。於此’應留意本發明之粒子為金屬間化合物，並非非晶形合金或膠體粒子。本發明之粒子為金屬間化合物，係如實施例所驗證般，可由粉末1射線繞射測定之結果予以確認。尚且’本說明書中’所謂「金屬間化合物」係指2種以上之金屬元素依簡單的整數比進行結合*成的化合物，並 312XP/發明說明書(補件)/97·01/96Β5322 200829331 頒不與成分金屬元素不同之特有的物理•化學性質的化合物。 ^ 根據 J〇urnal of Phase Equilibria, 12(1)，199卜 •作為由铑及碲所形成之金屬間化合物，顯示有例如 Rh3Te2、RhTeu、RhlTei、Rh3Te4、Rh3Te8# 之存在。如此，本發明之铑-碲金屬間化合物粒子，其铑與碲之原子比較佳為3 : 2〜3 : 4，更佳為3 : 2、3 : 4或1 : 1之任一種。 _米本發明之鍺-碲金屬間化合物粒子的形狀並無限制，通吊係平均粒徑lnm以上、1〇〇nm以下左右之一次粒子進行砝集而形成二次粒子的凝集體。此係屬於與粒子表面由保屢基所覆蓋之膠體粒子完全不同的形狀。另外，本發明之铑-碲金屬間化合物粒子的粒子徑，較佳為6nm以上、16nm以下。本發明之錄-碲金屬間化合物粒子的用途，並無限制，例/α以下所說明般，可廣泛地使用作為氧化反應用之觸媒 _ (氧化觸媒）。其中，適合使用作為醯氧基化反應用觸媒。 [3·氧化觸媒] 在將本無明之錢-碲金屬間化合物粒子使用作為氧化觸媒％，亦可直接使用藉還原反應所得之錄—碲金屬間化合物粒子。此情況下，可於還原反應後之反應液中加入氧化 •反應之反應基質，而進行氧化反應。 • 另外，對於藉還原反應所得之铑-碲金屬間化合物粒子，除了貫施上述任意之後處理（分離、洗淨、乾燥、熱處理等）之外，亦可供於作為氧化觸媒的用途。 312ΧΡ/發明說明書(補件)/97-01/96135322 26 200829331 ’由提升一次粒子之分散性的觀點而言，較佳 :务明之鍺-碲金屬間化合物粒子载持於二、：的肤離，伯田H 4 、夕孔貝戟脰上刃狀L使用作為氧化觸媒。多孔ί载：:::發明之錄’金屬間化合物粒子载持於 _ 的蝴物此簡稱為「本發明之氧化Further, the pH adjuster may be used alone or in combination of two or more. Any one of the steps of adjusting the pH by using a pH adjuster in any combination may be adjusted to the above-mentioned predetermined range while keeping the metal salt from being precipitated. Specific one can be. There are no restrictions. In the state in which the reduction of the reaction liquid can be carried out, the following steps can be exemplified, and before the solution of the metal salt solution is prepared by dissolving the strontium salt, the sulfonium salt and the cleavage agent in the solvent, respectively. The pH of each solution was individually adjusted by a Qiu adjuster. • After the = metal salt solution containing (4), cerium salt and the wrong agent is prepared, the metal salt solution of the metal salt solution is adjusted by the pH adjusting agent before the reduction reaction, and the reduction reaction is not carried out. After adding a reducing agent under temperature conditions (temperature conditions not exceeding the above-mentioned predetermined temperature range), the pH adjusting agent is adjusted by heating the reaction liquid to a temperature condition (temperature condition within the above-mentioned predetermined temperature range) during which the reduction reaction is carried out. The pH of the reaction solution. Further, the pH adjustment by the pH adjuster can be carried out once or in two or more steps. [1 -6· Post-treatment] By the above reduction reaction, ruthenium-iridium intermetallic compound particles 312 ΧΡ / invention specification (supplement) / 97-〇 1/96135322 22 200829331 can be obtained. The obtained ruthenium-iridium intermetallic compound particles can be used as they are, and can be subjected to separation, washing, drying, heat treatment, etc., as needed. The method of separating the obtained ruthenium-iridium intermetallic compound particles from the reaction liquid, and the soaking &' can be, for example, an over-concentration method using crepe paper or crepe paper, separation, precipitation separation (decantation method, etc.), and the like. Among them, filtration and methods are generally used. These methods may be used singly or in combination of two or more kinds in any combination. The solvent (washing solvent) in the case where the ruthenium-ruthenium intermetallic compound particles are removed from the knives is not the same as the ruthenium-iridium intermetallic compound granules: the reactants or the two-way intermetallic compound particles. There is no limitation on the adverse effect, and for example, a solvent of the same kind as the solvent which can be used is usually used. Further, the "washing solvent" may be used alone or in combination according to any combination and ratio. Drying and drying the hoof's hoof intermetallic compound particles after the second gentleman or washing) can be dried under normal pressure and reduced pressure (or vacuum). The conditions of the vicinity (Μ or how many additions and subtractions) are as a drying method, for example, a rotary drying like a stationary rotary evaporator such as a furnace, a fixed bed gas, a moving = two, a spray drying such as a dryer, In the case of a belt-type furnace or a dry type, it is possible to use a 帛 ace ace = = , , , , , , , , 。。。。。。。。。。。。。。。。。。。。。。。。。。 As a gas that flows during drying, • (4), by _ 312XP/^H^W(M#)/97-〇l/96135322 23 200829331 =,: Air, nitrogen, etc. are often used. Further, in the case of performing enthalpy, intermetallicization: in the case of air treatment of the particles, hydrazine can be added to the gas to be circulated during drying. The === is used for the desired use of the carbon-hoof metallization without the hydrogen treatment after drying, and is preferably gas from the viewpoint of economy. And /: ^ soil phantom moon gas 2 with any kind, the village recorded combination and ratio (4) 2 like the combination of t, quick drying, from the point of view, 'preferably in the circulation of the water . There is no special restriction on the temperature during drying. == The agent is dried for two times. :: Two drying or dry-welding with the pressure increase of the 诏诏 ^. ^r... ffl Dry. In the case of heat drying, dry fresh is dried by heating. . The following range. In the case of (9)t / usually 40 c or more, the outline, the brother, the anti-ducking machine is used for the prevention of the heart, the drama of the Buddha, and the temperature below the net solvent. deal with. ^The public media or washing in the dry 锗碲碲碲 _ _ _ 作为作为作为作为作为作为作为作为 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ , kiln or rotating..., knowing the % conversion, fixed, ancient ^, etc., can be used. The selection of the transfer drying method of the machine wood, the belt-type furnace, etc. is determined depending on the amount of processing, etc., regardless of the use of any - 312XP / invention manual (supplement) machine _6135322 ^ 200829331 drying method, it is preferable to let the gas flow Dry on one side. As a gas to be circulated, it is preferably a gas containing no oxygen. Specific examples thereof include an inert gas such as nitrogen, argon or helium; hydrogen or the like. These gases may be used singly or in combination of two or more kinds in any combination and in any ratio. Preferably, nitrogen or hydrogen is used alone or as a mixture. The lower limit of the temperature of the heat treatment is usually 100 ° C or more, preferably 丨 5 (rc or more, more preferably 200 ° C or more, still more preferably 3 ° C or more. The upper limit of the heat treatment temperature is usually 锗-碲When the melting point of the intermetallic compound particles is not higher than the melting point of the intermetallic compound particles, the ruthenium-iridium intermetallic compound particles are doubled due to sintering, and the surface area of the metal is lowered. Therefore, when the obtained ruthenium-iridium intermetallic compound particles are used for catalyst use, The activity of the catalyst is lowered. Therefore, from the viewpoint of enhancing the activity of the catalyst, the upper limit of the heat treatment temperature is usually not more than °c, preferably 60 (src or less, more preferably 5 〇 (rc or less. [2 · money-碲Intermetallic compound particles] The ruthenium-iridium intermetallic compound particles obtained by the production method of the present invention (hereinafter referred to as "the ruthenium-iridium intermetallic compound particles of the present invention" or simply referred to as "X-month particles") are usually High-purity intermetallic compounds formed by ruthenium and osmium. Here, it should be noted that the particles of the present invention are intermetallic compounds, not amorphous alloys or colloidal particles. The particles of the present invention are intermetallic compounds, as in the examples. verification In general, it can be confirmed by the results of the powder 1 ray diffraction measurement. In the present specification, the term "intermetallic compound" means a compound in which two or more metal elements are bonded in a simple integer ratio, and 312XP/invention Instruction manual (supplement) /97·01/96Β5322 200829331 A compound of physical and chemical properties that is not unique to the constituent metal elements. ^ According to J〇urnal of Phase Equilibria, 12(1), 199 The intermetallic compound formed by ruthenium exhibits the presence of, for example, Rh3Te2, RhTeu, RhlTei, Rh3Te4, and Rh3Te8#. Thus, the ruthenium-iridium intermetallic compound particles of the present invention preferably have an atom of ruthenium and osmium of 3: 2~ 3: 4, more preferably 3: 2, 3: 4 or 1 : 1. Any shape of the 锗-碲 intermetallic compound particles of the present invention is not limited, and the average particle diameter of the hanging system is 1 nm or more, 1 The primary particles of about 〇〇 nm or less are collected to form agglomerates of secondary particles, which are completely different from the colloidal particles whose surface is covered by the protective group. Further, the ruthenium-iridium metal of the present invention Chemical The particle diameter of the particles is preferably 6 nm or more and 16 nm or less. The use of the ruthenium-iridium intermetallic compound particles of the present invention is not limited, and as described in the following example, α can be widely used as a contact for oxidation reaction. Medium _ (oxidation catalyst), which is suitably used as a catalyst for the oximation reaction. [3. Oxidation catalyst] The sensible money-ruthenium intermetallic compound particles are used as the oxidation catalyst%, and may also be used. The ruthenium intermetallic compound particles obtained by the reduction reaction are directly used. In this case, an oxidation reaction can be carried out by adding a reaction substrate of the oxidation reaction to the reaction liquid after the reduction reaction. • In addition, the ruthenium-iridium intermetallic compound particles obtained by the reduction reaction can be used as an oxidation catalyst in addition to any of the above-mentioned subsequent treatments (separation, washing, drying, heat treatment, etc.). 312ΧΡ/Invention Manual (Supplement)/97-01/96135322 26 200829331 'From the viewpoint of improving the dispersibility of primary particles, it is preferred: the 锗-锗 intermetallic compound particles are carried on the second, : , Ueda H 4 and U.S. sinensis are used as an oxidation catalyst. Porous 载::::Inventory of the invention, the intermetallic compound particles are carried on the _ butterfly, which is simply referred to as "the oxidation of the present invention.

，為载體，並無限制，通常係使用無機多孔體機多孔體之例子，可與办丨马… 化錯(_、氧化=0 …氧化乳化銘（Ah〇3)、二氧化鈦（Ti〇2)、舻仆坊，、氮化石夕(siN)等。此等可單獨使用二 2種以上— 為载體較么係活性碳、二氧化矽（si02)。 j需要亦可將鋪進行表面處理後再❹。例如，氧化石夕（Si〇2)表面以碳進行塗層後再使用。As a carrier, there is no limitation. Usually, an example of using an inorganic porous body machine porous body can be used, and it can be used to solve the problem. (_, oxidation = oxidative emulsification (Ah〇3), titanium dioxide (Ti〇2) ), 舻坊坊, 氮化夕夕 si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si si. After that, for example, the surface of the oxidized stone (Si〇2) is coated with carbon and then used.

將本，明之錢-碲金屬間化合物粒子载持於载體上的方 /、’亚m限定’例如，可於不進行還原反應之溫度 ^述規定溫度範圍之温度）下混合金屬鹽溶液與還原劑後’使所得之混合溶液含浸至載體的細孔内，藉由加敎至進行运原反應之溫度（上述規定溫度範圍内的溫度），^還原反應進行而合成本發明之鍺_碲金屬間化合物粒子，並使其載持於载體的細孔内。、本發明之觸媒較佳係於液相反應下的使用。亦即，較佳係在反應時’基質及氧親核劑中之至少一者以上為液狀：與本發明之氧化觸媒接觸。 312XP/發明說明書(補件)/97-01/90135322 27 200829331 fj- 1 /、，本發明之氧化觸媒，若應用於將氧親核劑氧化性 :加成在烯烴或芳香族化合物上之反應二使用其之氧化性加成生成物的製造方法上，則可、二到#乂:效果，故較佳。此情況下，氧親核劑係對於例如烯t f方香族化合物之不飽和結合部位或芳香族之側鏈進行氧化性加成反應。作2可使用本發明之氧化觸媒的氧化性加成反應的例春子，可舉例如由烯烴之氧化所進行的醛合成；氧氯化 (j)xyChiQrinati()n)或氧化性酿氧基化、氧化性氰基化、 1化性烷氧基化等之氧陰離子化(oxyanionizatiorO ;烯烴及/或芳香族之偶合反應；氧化性羧基化等。、作為氧氯化之具體例，可舉例如來自乙烯之氯化乙烯合成、來自丙烯之烯丙基氣化物合成、來自丁二烯之二氯丁成纟自異戊二稀之二氯甲基丁烯合成、來自苯之氯苯合成、甲苯或二甲苯之側鏈氯化等。 _ 作為氧基化之具體例，可舉例如來自乙烯而以醋酸乙烯酯為代表之醯氧基乙烯合成、來自丁二烯之二醯氧基丁烯t成、來自異戊二烯之二醯氧基甲基丁烯合成、來自苯之齜氧基苯合成、曱苯或二曱苯之側鏈醯氧基化等。作為氰基化之具體例，可舉例如來自乙烯之丙烯腈合成來自丁一烯之二氰基丁烯合成、來自異戊二烯之二氰 .基甲基丁烯合成、來自苯之氰基苯合成、甲苯或二甲苯之側鏈氰基化等。作為烧氧基化之具體例，可舉例如來自乙烯之曱基乙基 312XP/發明說明書(補件)/97-01/96135322 28 200829331 醚合成、來自丁二烯之二烧氧基丁埽合成、來自異戍二稀之二燒氧基曱基丁烯合成、來自苯之烧氧基苯合成、甲苯或二曱苯之侧鏈烷氧基化等。作為偶合反應之具體例，可舉例如來自苯之聯苯合成、來自曱本之甲基苯二聚物合成、來自醋酸乙烯酯之二乙醯氧基丁二婦合成、來自苯乙烯與苯之二苯乙稀合成、來自苯乙婦，苯乙烯與苯之三苯基苯及四苯基苯合成等。作為氧化性絲化的具體例，可舉例如來自乙烯盘一氧化碳之丙烯酸合成、來自一氧化碳與醇的草酸二酯合成、來自^烯與-氧化碳及醇之琥轴酸二酉旨合成、來自丁二稀與一氧化矽及醇之己二酸酯類之合成等。作為酸合成的具體例’可舉例如來自乙婦的乙酸合成等。，中’本發明之氧化觸媒，若使用作為液相氧化性酿氧基化及/或燒氧基化反應用的觸媒，則活性極高而較佳。 =者，本發明之氧化觸媒即使應用於將氧親核劑氧化性有側鏈燒基之芳香族化合物上的反應、與使用其 Ί加成生成物之製造方法上，其效果亦高。此情況所鄰接的碳上。也加成至側鏈燒基之芳香環上 [4·氧化性加成生成物之製造方法] 劑由使用明之氧化觸媒之若夭_至烯烴或方香族化合物（或具有側鏈烷基曰矢b合物）上的反應’而製造氧化性加成生成物的 312XP/發明說明書(補件)/97-01/96135322 29 200829331 ^法i以下稱為「本發明之氧化性加成生成物之製造方法」進行况明。产本發明之氧化性加成生成物之製造方法，係於本發明之 =觸媒及分子狀氧的存在下，藉由使氧親_氧化性地烯烴或芳㈣化合物上’而製造氧化性加成生成物本發明之氧化性加成生成物之製造方法巾，使用作為原Mixing the metal salt solution with the square/, 'sub-m defined' of the carbon-ruthenium intermetallic compound particles supported on the carrier, for example, at a temperature at which the temperature of the reduction reaction is not carried out After the reducing agent, the obtained mixed solution is impregnated into the pores of the carrier, and the ruthenium of the present invention is synthesized by adding to the temperature at which the original reaction is carried out (the temperature within the above-mentioned predetermined temperature range). The intermetallic compound particles are carried in the pores of the carrier. The catalyst of the present invention is preferably used in the liquid phase reaction. That is, it is preferred that at least one of the substrate and the oxygen nucleophile at the time of the reaction is in a liquid state: it is in contact with the oxidation catalyst of the present invention. 312XP/Invention Manual (Supplement)/97-01/90135322 27 200829331 fj-1, the oxidation catalyst of the present invention, if applied to oxidizing an oxygen nucleophile: addition to an olefin or an aromatic compound In the method for producing the oxidative addition product of the second reaction, it is preferred to use the method of the second embodiment. In this case, the oxygen nucleophile is subjected to an oxidative addition reaction to, for example, an unsaturated binding site of an olefinic t-fragrance compound or an aromatic side chain. Examples of the oxidative addition reaction using the oxidation catalyst of the present invention include, for example, aldehyde synthesis by oxidation of an olefin; oxychlorination (j) xyChiQrinati()n) or an oxidative oxy-oxyl group. Oxidation (oxyanionizatior O; coupling reaction of olefin and/or aromatic; oxidative carboxylation; etc.), such as oxidative cyanation or mono-alkoxylation, as a specific example of oxychlorination, for example Such as the synthesis of ethylene chloride from ethylene, the synthesis of allyl gasification from propylene, the synthesis of dichloromethylbutene from isobutadiene, the synthesis of chlorobenzene from benzene, The side chain of toluene or xylene is chlorinated, etc. _ As a specific example of oxylation, for example, a decyloxy group represented by ethylene and represented by vinyl acetate, and a dimethoxy olefin butene derived from butadiene t, synthesis of dimethoxymethylbutene from isoprene, synthesis of benzylbenzene from benzene, side chain oximation of fluorene or diphenyl, etc. As a specific example of cyanation For example, the synthesis of acrylonitrile from ethylene to dicyanobutane from butadiene Synthesis of ene, synthesis of dicyanylmethylbutene from isoprene, synthesis of cyanobenzene from benzene, side chain cyanation of toluene or xylene, etc. As a specific example of the alkoxylation, an example is exemplified. Such as thiol ethyl 312XP from ethylene / invention instructions (supplement) / 97-01/96135322 28 200829331 ether synthesis, synthesis of butadiene from butadiene, alkoxylate from isoindole Synthesis of mercaptobutene, synthesis of alkoxybenzene derived from benzene, side chain alkoxylation of toluene or dinonylbenzene, etc. Specific examples of the coupling reaction include, for example, biphenyl synthesis from benzene, from Sakamoto Synthesis of methylbenzene dimer, synthesis of ethylene oxide from vinyl acetate, synthesis of styrene and benzene diphenylethylene, benzene, styrene and benzene triphenylbenzene Tetraphenylbenzene synthesis, etc. Specific examples of the oxidative silking include, for example, acrylic acid synthesis from ethylene disk carbon monoxide, oxalic acid diester synthesis from carbon monoxide and alcohol, and aromatic acid derived from olefin and carbon monoxide and alcohol. Synergistic synthesis, from dibutyl sulphate and cerium oxide and alcohol The synthesis of the adipate esters, etc. As a specific example of the acid synthesis, for example, acetic acid synthesis derived from a woman, etc., can be used as the oxidation catalyst of the present invention. Or the catalyst for the alkoxylation reaction is extremely active and preferably. If the oxidation catalyst of the present invention is applied to an aromatic compound which oxidizes an oxygen nucleophile with a side chain group. Moreover, the effect is also high in the production method using the ruthenium addition product. In this case, the adjacent carbon is added to the aromatic ring of the side chain alkyl group. [4. Manufacture of oxidative addition product Method 312XP/Invention Manual for Producing Oxidative Addition Products by Using the Reaction of the Oxidation Catalyst to the Olefin or Fragrance Compound (or Has a Side Chain Alkyl Group B Compound) (Supplement) / 97-01/96135322 29 200829331 ^ Method i Hereinafter, the "manufacturing method of the oxidative additive product of the present invention" will be described. The method for producing an oxidative addition product of the present invention is produced by oxidizing an oxo-oxidative olefin or an aromatic compound in the presence of a catalyst and molecular oxygen of the present invention. Addition product The method for producing an oxidative addition product of the present invention is used as a raw material.

t!㈣烴（以下稱為「原料_」）若為不對反應造成不良曰一者貝]其種類並热限制，較佳為直鍵或分支狀之鍵狀 ^烴，或單環、多環或縮合環式之環烯烴，更佳為直鍵或分支狀之鏈狀烯烴或單環的環烯烴。原料烯烴在不對本發明之氧化反應造成不良影響的範圍内，亦可具有取代基。作為取代基之例子，可舉例如烯丙基、芳基、鹵基、硝七氰基、胺基、醯胺基、烷氧基、醯基、羧基、曱醯基、醯氧基、羥基、羥基曱基等。一原料稀煙所具有之上述取代基的數量，係每一分子烯火工通系為0以上，且通常為3以下、較佳2以下、更佳 1以下。在原料烯烴具有2個以上取代基的情況，其等互相可為相同或相異。、直鏈或分支狀之鏈狀烯烴的碳數，通常為2以上，且通常為30以下、較佳12以下、更佳1〇以下的範圍。單％、多裱或縮合環式之環烯烴的碳數，通常為4以上、較佳5以上、更佳6以上，且通常為3〇以下、較隹 312XP/發明說明書(補件)/97-01/96135322 30 200829331 12以下、更佳1 〇以下的範圍。尚且，在原料烯烴具有取代基的其等取代基的整體碳數為滿^上述範圍。—係亦包括 …例’可舉例_、丙烯、己二二丁細、環戍坤、環己稀、環庚稀、丁二稀、環其中’作為原料烯烴，較佳為共軛二烯。二辇、、士 - π / , 』—佈）、2,3一一甲基丁二烯 ’）戊一烯（1，3 —戊二烯）、戊二稀、環己二烯等)[ 細，狀共軛二烯(環烷基取，、中’作為共輛二烯，較佳為丁二烯、戊二烯代丁一烯’特佳為丁二烯或烷基取代丁二烯。其中’作為原料烯煙，較佳為環烯烴。 :為環烯烴之具體例’可舉例如 _等’特佳為環己烯。尚且’此等原料烯烴可單 . 合及比例將2種以上組合^使用任—種，亦可依任意組本=之氧化性加成生成物之製造方法中，使用作為原 =之方日族化合物（以下稱為「原料芳香族化合物」），若為=對反應造心良料者，财_並無關。可香族化合物。於縮合環的情況，其環 f通吊為2以上，且通常為10以下、較佳6以下、更佳以下。此等之中’作為原料芳香族化合物，較佳係單環 312XP/發明說明書(補件)/97·01/96135322 200829331 更佳為單環的芳香族化或2環之縮合環的芳香族化合物合物。 ==族化合物在不對本發明之氧化反應造成不良〜曰的犯圍内，亦可具有取代基。 ^為取代基之例子，可舉例如自縣、烯丙基、芳基、齒基、石肖基、氰基、胺基、酿胺基、烧氧基、酿基、敌基、曱醯基、酿氧其、、# 皿虱基、經基、羥基曱基中選出之至少一個取基0 、(4) Hydrocarbons (hereinafter referred to as "raw materials") are not restricted to the reaction, and their types are thermally restricted, preferably linear or branched, or monocyclic or polycyclic. Or a condensed cyclic cycloolefin, more preferably a linear or branched chain olefin or a monocyclic cycloolefin. The raw material olefin may have a substituent in a range which does not adversely affect the oxidation reaction of the present invention. Examples of the substituent include an allyl group, an aryl group, a halogen group, a nitrico-7-cyano group, an amine group, a decylamino group, an alkoxy group, a decyl group, a carboxyl group, a decyl group, a decyloxy group, a hydroxyl group, and the like. Hydroxy thiol and the like. The number of the above substituents in the raw material flue gas is 0 or more per molecule of the olefin fire passing system, and is usually 3 or less, preferably 2 or less, more preferably 1 or less. In the case where the raw material olefin has two or more substituents, the mutually different phases may be the same or different. The linear or branched linear olefin has a carbon number of usually 2 or more, and is usually 30 or less, preferably 12 or less, more preferably 1 or less. The carbon number of the mono-, poly- or condensed cyclic cycloolefin is usually 4 or more, preferably 5 or more, more preferably 6 or more, and usually 3 or less, compared to 隹 312XP / invention specification (supplement) / 97 -01/96135322 30 200829331 12 or less, preferably 1 〇 or less. Further, the total carbon number of the substituent such as the substituent of the raw material olefin is in the above range. The system also includes, for example, propylene, hexamethylene dibutyl, cyclohexanthene, cyclohexylene, cyclopentylene, butadiene, and a ring thereof as a raw material olefin, preferably a conjugated diene. Diterpenoids, s - π / , 』 - cloth), 2,3-monomethylbutadiene ') pentylene (1,3-pentadiene), pentane diene, cyclohexadiene, etc. [ a fine, conjugated diene (cycloalkyl group, medium 'as a total of a diene, preferably butadiene, pentadiene butadiene) is preferably a butadiene or alkyl substituted butadiene In particular, 'as a raw material olefin, preferably a cycloolefin. A specific example of a cyclic olefin' may, for example, be a hexene olefin, etc. Further, 'the raw materials olefins may be singly and in combination. In the above method, the oxidizing addition product of any group is used, and the Japanese compound (hereinafter referred to as "raw material aromatic compound") is used as the original method. = It is not necessary for the reaction to be good. It can be a fragrant compound. In the case of a condensed ring, the ring f is entangled to 2 or more, and usually 10 or less, preferably 6 or less, more preferably the following. As a raw material aromatic compound, it is preferably a single ring 312XP / invention specification (supplement) / 97·01/96135322 200829331 more preferably a single ring aromaticization The aromatic compound of the condensed ring of the 2-ring. The compound of the == group may have a substituent in the case of not causing the oxidation reaction of the present invention to be unfavorable to 曰. ^ As an example of the substituent, for example, from the prefecture , allyl, aryl, dentate, schlossyl, cyano, amine, amide, alkoxy, aryl, enantiomer, sulfhydryl, ethoxylate, ##虱基, 经基, At least one selected from the group consisting of hydroxy fluorenyl groups

’、芳3無化合物所具有之上述取代基的數量，係每一 :子芳香族化合物，通常為。以上，且通常為3以；、較佺2以下、更佳1以下。在原料芳香族化合物具有2個以 Um㈣互相可為相同或相異。」乍為原料方香族化合物之具體例，可舉例如曱苯、乙基 ^ 4 一曱笨、間二曱苯、對二曱苯、二乙基苯、鄰氯; =、間氣甲苯、對氯甲苯、二氯甲苯、鄰石肖基甲苯、間硝基:苯、制基甲苯、鄰甲氧基甲苯、間甲氧基甲苯、對 :乳基甲苯、鄰苯氧基甲苯、間苯氧基甲苯、對苯氧基甲，4甲苯酉夂、甲苯酸、對甲苯酸、鄰曱苯曱醛、間甲苯甲酸董子甲苯甲醛、鄰甲酚、間甲酚、對甲酚、鄰甲吴苄醇、間甲基苄醇、對甲基苄醇等。土尚且，此等之原料芳香族化合物可單獨使用任一種，亦可依任意組合及比例將2種以上組合使用。乳求核劑係對上述例示之原料烯烴或原料芳香族化人物’例如於其不飽和鍵結部位進行氧化性加成反應。° 312XP/發明說明書(補件)/97·〇1/96135322 32 200829331 作為本發明之氧化性加成生成物之製造 =，可舉例域㈣二烯與賴及分子狀氧應之不飽和H酯时法；使料二職醇及== :反應广製造對應之不飽和乙二醇二醚的方法;使環己烯 '、羧酉夂及刀子狀氧反應而製造對應之醯氧基環己婦的方法；使烧絲_酸及分子狀氧反應而製烷基苯的方法等。 n乳丞 X上述具體例中’共軛二烯較佳係由上述之丁二烯、戊二烯及院基取代丁二烯中選擇。又，魏酸較佳為贈酸。，依以下之記載’係以上述具體例中，藉由使共軛二烯與羧酸及分子狀氧反應並進行醯氧基化，而製造所對應之不飽和乙二醇二酯的情況為主，詳細說明本發明之氧^性加成生成物之製造方法。作為屬於反應原料之共輛二烯，可使用上述般之丁二烯、烷基取代丁二烯（異戊二烯（2-甲基-l 3一丁二烯）、 ⑩2, 3-一曱基丁二烯等）、戊二烯（1，3-戍二烯）、ι，4一己二烯、環狀共軛二烯（環戊二烯、環己二烯等）等。其中，較佳為丁二烯、戊二烯、烷基取代丁二烯。屬於反應原料之共軛二烯並不一定為質純者，亦可含有如氮氣般之惰性氣體；曱烷、乙烷、丁烷等之飽和烴；丁 - 烯等之不飽和烴等之其他成分。具體而言，相對於共軏二 • 烯及其他成分之共軛二烯的比例，通常為1 〇重量％以上、較佳50重量％以上、更佳80重量％以上、特佳90重量％以上。 312XP/發明說明書(補件)/97-01/96135322 33 200829331 •作為屬於其他反應原料的錢，可使用脂肪族緩酸、月匕 %族羧酸、芳香族羧酸等任意者。1 曰 / 八τ 价丄系万面，輪㈣使用低級（碳數4以下）脂肪族單㈣。作為具體例，可舉例如醋酸、丙酸、赂酸、異赂酸等，由反應性及價格之觀點而言，較佳為醋酸。 ° 屬於反應原料线酸，通f係兼作為溶媒，視需要可於反應中使用惰性之有機溶媒，例如飽和煙溶 =其中’較佳係反應溶媒之5G重量％以上為反應原: 羧酸。竣酸之使用量係相對於共輛二烯i莫耳，通以上、100莫耳以下之範圍。吳斗本發明之氧化性加成生成物之製造方法中，係使用分子狀氧之氣體’較佳為於液相下將上述原料（共辆及羧酸）與固體觸媒進行接觸。歸狀氧之氣體係指純氧或氧與惰性氣體之此口乳脰。作為惰性氣體，可舉例如氮、氬、氦又，混合氣體亦包括空氣。 x、分子狀氧可依與惰性氣體之任意的混合比例，於 =屢狀態Γ供給至反應系統中，但較佳係氧濃度不為反應糸統内之氣相部成為爆發組成的範圍。 -般而言’氧化反應係氧分麗越高而對反應速度越有利，故更佳係在其限定之範圍内依者旦6 n人站㈣円依考里文全率之最大漠度進灯供給。然而，關於較空氣更高之氧濃度，其需要用以促進燃燒反應和氧高濃度化的設備，且由於高濃度氧氣體 312XP/發明說明書(補件)/97-01/96135322 200829331 本身的危險性亦增加，故除了特別要求反應速度的情況，一般係不使用。另外，氧分壓係視所供給之氧濃度、反應系統中之組成與反應麼力、溫度而決定。本發明之氧化性加成生成物之製造方法，可依分次式、連續式之任一方法進行。另外，作為反應方式，可採用固定床式、流動式、㈣槽式等任意方式，工業上較佳為固定床式。反應溫度通常可依赃以上之溫度進行，若考慮反應速度及副生物生成等，較佳依4(rc以上、12(rc以下之^ 度。 /皿另外，反應壓力可為常壓、加壓之任一種。為了提内反應速度\較佳為加壓，但有反應設備㈣變高的傾向。若考慮此等’則適合的反應壓力，為常壓（ lOOkgf/cm2以下之範圍。」乂上、烯尚且，於上述步驟中，藉由使用環己稀代替則可製造醯氧基環己烯。此情況下，作為原料所使用之環己烯有許的環己燒、苯等，又，含有微量的水亦無妨例如些以上、較佳90重量己細的純度通常為5。重量% 另外，於上述步驟中，藉由則可製造醯氧基烷基笨。 ^ ^ ㈢共軛二埽， 312XP/發明說明書(補件)/97-01/96135322 35 200829331 此情況下’作為原料所使用之烧基苯，許的苯等，又，含有微量的水亦無妨。&有例如些其中，此情況下，原料之縣苯之純度較的高。具體而言，原Μ夕γ = e h丄— 你馮杲私度以上、較佳90重量％以上。勹Μ重里/〇則可製造再者’於上述步驟中’藉由使用醇代替緩醆不飽和乙二醇二醚。乙 >醇的種類亚無特別限定，工業上可使用例如醇、丙醇、異丙醇等之碳數4以下的低級醇。 [實施例] 以下，使用貫施例更詳細地說明本發明，但本發明在不超過其要旨之下，並不限定於以下實施例。 Λ [實施例1] 對蒸餾水加入0·15ιη〇ι之氯化铑及0 30mm〇1之丨，3一二羥基-4-(2- π比啶基偶氮）苯 ⑩（1，3-dihydroxy-4-（2-Pyridylazo)benzene)(簡稱 pAR ·· 分子式CuH9〇2N3)，再加入氫氧化鈉而將pH調整為13，藉此使氯化鍺與PAR溶解，調製成含铑溶液1〇ml。以此^ 為A溶液。又，對蒸餾水加入0.40mmol之檸檬酸使其溶解後，加入O.lOminol之碲酸使其溶解，調製成含碲溶液1〇ml。以此作為B溶液。其-人，混合A溶液與B溶液，於此加入蒸顧水與氫氧化鈉而調整為PH13並作成總量48ml後，以充分時間進行混 312XP/發明說明書(補件)/97-01/96135322 36 200829331 合，再加入80%飽水肼溶液2ml，於70X：進行還原3小時。將藉還原所得之黑色粉末於氮環境氣體中進行過濾、水 . 洗，於氮氣流下以90°C乾燥1小時後，升溫至150X：並保持1小時後，冷卻至室溫，得到化合物粉末（實施例1之化合物粉末）。將實施例1之化合物粉末0. 015g添加至已裝有5Og醋酸之100ml四口燒瓶中，於對醋酸層進行氮吹入之下升溫至90 °C。停止氮吹入，代替其分別將1，3-丁二烯依 ⑩10ml/min之流量、將10%氧/氮混合氣體依25ml/min之流量吹入，使反應開始。反應3小時後，將吹入氣體再次切換為氮，冷卻至室溫，過濾出化合物粉末。將反應液依氣體層析法進行分析，結果生成了 2. 9 9匪ο 1 之1，4-二乙醯氧基-2-丁烯。另外，以感應輕合電漿質量分析裝置（Induct i ve 1 y coupled plasma mass spectrometry :以下簡稱為 φ 「ICP-MS」）測定溶解於反應液中之铑的濃度，結果為 21 ppm。相較於後述之比較例3，可知抑制了铑的溶出。 [實施例2] 將實施例1之化合物粉末於氮氣流中升溫至150°C後，使流通之氣體從氮切換為氫，再升溫至400°C並保持2小 .時，藉此進行熱處理，其後，使流通的氣體再切換為氮而冷卻至室溫，得到化合物粉末（實施例2之化合物粉末）。對實施例2之化合物粉末進行粉末X射線繞射測定。將所得之粉末X射線繞射圖案與RhsTe2之標準波峰一同示於 312XP/發明說明書(補件)/97-01/96135322 37 200829331The number of the above substituents which the aryl 3 has no compound is, usually, a subaromatic compound. The above is usually 3 or more, more preferably 2 or less, still more preferably 1 or less. In the case where the raw material aromatic compound has two, Um (tetra) may be the same or different from each other. Specific examples of the starting material aromatic compound include, for example, anthracene, ethyl 4, anthracene, m-diphenyl, p-diphenyl, diethylbenzene, o-chloro; p-Chlorotoluene, Dichlorotoluene, O-Shishatoluene, m-Nitro: Benzene, Molybdenum toluene, o-methoxytoluene, m-methoxytoluene, p-:toluene toluene, o-phenoxytoluene, m-phenoxy Toluene, p-phenoxymethyl, 4-toluene, toluic acid, p-toluic acid, o-quinone furfural, m-toluic acid, toluene-formaldehyde, o-cresol, m-cresol, p-cresol, o-methyl benzyl Alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, and the like. In addition, any of the raw material aromatic compounds may be used singly or in combination of two or more kinds in any combination and in any ratio. The milk nucleating agent is subjected to an oxidative addition reaction to the above-exemplified raw material olefin or raw material aromatized human, for example, at its unsaturated bonding site. ° 312XP/Invention Manual (Supplement)/97·〇1/96135322 32 200829331 As the production of the oxidative addition product of the present invention =, the domain (4) diene and the unsaturated oxygen ester of the molecular oxygen should be exemplified. Time method; method for preparing second-acting alcohol and ==: reaction to produce corresponding unsaturated ethylene glycol diether; reacting cyclohexene', carboxy oxime and knife-shaped oxygen to produce corresponding oxirane ring A method for producing alkene benzene by reacting a calcined acid with an acid and a molecular oxygen. n 乳丞 X In the above specific example, the conjugated diene is preferably selected from the above-mentioned butadiene, pentadiene and the tert-substituted butadiene. Further, the formic acid is preferably an acid. According to the following description, in the above specific example, the corresponding unsaturated diethylene glycol diester is produced by reacting a conjugated diene with a carboxylic acid and a molecular oxygen and performing oximation. The method for producing the oxygenated additive product of the present invention will be described in detail. As the total of the diene which is a reaction raw material, the above-mentioned butadiene, alkyl substituted butadiene (isoprene (2-methyl-l 3-butadiene), 102, 3-anthracene can be used. Butadiene, etc.), pentadiene (1,3-decadiene), iota, 4-hexadiene, cyclic conjugated diene (cyclopentadiene, cyclohexadiene, etc.). Among them, butadiene, pentadiene, and alkyl-substituted butadiene are preferred. The conjugated diene belonging to the reaction raw material is not necessarily pure, and may contain an inert gas such as nitrogen; a saturated hydrocarbon such as decane, ethane or butane; or an unsaturated hydrocarbon such as butane-ene. ingredient. Specifically, the ratio of the conjugated diene to the conjugated hexene and other components is usually 1% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. . 312XP/Inventive Manual (Supplement)/97-01/96135322 33 200829331 • As the money for other reaction materials, any of aliphatic acid, sulphuric acid, aromatic carboxylic acid, and the like can be used. 1 曰 / 八丄万 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Specific examples thereof include acetic acid, propionic acid, citric acid, and isonic acid. From the viewpoint of reactivity and price, acetic acid is preferred. ° is a reaction raw material line acid, and the system is used as a solvent. If necessary, an inert organic solvent can be used for the reaction, for example, saturated smoke solution = wherein 5% by weight or more of the preferred reaction solvent is a reaction product: a carboxylic acid. The amount of citric acid used is in the range of 100 m or less relative to the total amount of diene. In the method for producing an oxidative addition product of the present invention, a gas of molecular oxygen is used. It is preferred to contact the raw material (common vehicle and carboxylic acid) with a solid catalyst in a liquid phase. The gas system of oxidizing oxygen refers to the chylomicron of pure oxygen or oxygen and an inert gas. Examples of the inert gas include nitrogen, argon, and helium, and the mixed gas also includes air. x. Molecular oxygen may be supplied to the reaction system in an arbitrary state according to an arbitrary mixing ratio of the inert gas, but it is preferable that the oxygen concentration is not in the range of the explosive phase in the gas phase portion of the reaction system. - Generally speaking, the oxidation reaction is higher in oxygen and the more favorable the reaction rate, so it is better to be within the limits of the range of 6 n people (4). Light supply. However, with regard to higher oxygen concentrations than air, it is necessary to promote combustion reactions and oxygen concentration, and due to the high concentration of oxygen gas 312XP / invention manual (supplement) / 97-01/96135322 200829331 itself is dangerous Sex also increases, so it is generally not used except for the case where the reaction speed is specifically required. Further, the oxygen partial pressure is determined depending on the oxygen concentration supplied, the composition in the reaction system, the reaction force, and the temperature. The method for producing the oxidative addition product of the present invention can be carried out by any of a fractional method and a continuous method. Further, as the reaction method, any method such as a fixed bed type, a flow type, or a (four) tank type may be employed, and the industrial type is preferably a fixed bed type. The reaction temperature can usually be carried out according to the above temperature. When considering the reaction rate and the formation of by-products, it is preferably 4 (rc or more, 12 (cm or less). / Alternatively, the reaction pressure may be normal pressure or pressure. In order to increase the internal reaction rate, it is preferred to pressurize, but the reaction equipment (4) tends to be high. If these factors are considered, the suitable reaction pressure is normal pressure (the range of lOOkgf/cm2 or less.) In the above step, in the above step, decylcyclohexene can be produced by using cyclohexene instead. In this case, the cyclohexene used as a raw material has a ring-burning, benzene, etc., and It is also possible to use a trace amount of water, for example, more than 90 parts by weight, and the purity is usually 5% by weight. In addition, in the above step, a decyloxyalkyl group can be produced. ^ ^ (III) Conjugated埽, 312XP/Inventive Manual (Supplement)/97-01/96135322 35 200829331 In this case, 'burning benzene used as a raw material, benzene, etc., may contain traces of water. & Among them, in this case, the purity of the raw material benzene is relatively high. In terms of body, the original Μ γ = eh 丄你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你你杲杲杲杲杲杲杲The type of the alcohol is not particularly limited, and a lower alcohol having a carbon number of 4 or less such as an alcohol, propanol or isopropanol can be used industrially. [Examples] The present invention will be described in more detail, but the present invention is not limited to the following examples. Λ [Example 1] To a distilled water, ruthenium chloride of 0·15ιη〇ι and 0 30 mm〇1 were added. Thereafter, 1,3-dihydroxy-4-(2-pyridylazo)benzene (abbreviated as pAR ·· molecular formula CuH9〇2N3), Sodium hydroxide was added to adjust the pH to 13, whereby ruthenium chloride and PAR were dissolved to prepare 1 〇ml of a ruthenium-containing solution. This was used as the solution A. Further, 0.40 mmol of citric acid was added to the distilled water to dissolve it. After that, O.lOminol was added to make it dissolved, and it was prepared into a 碲ml solution containing hydrazine. This was used as the B solution. It-human, mixed A solution and B Liquid, after adding steam and sodium hydroxide to adjust to PH13 and make a total amount of 48ml, mix 312XP / invention manual (supplement) / 97-01/96135322 36 200829331 for a sufficient time, then add 80% 2 ml of a saturated hydrazine solution was subjected to reduction at 70X for 3 hours. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, washed with water, and dried at 90 ° C for 1 hour under a nitrogen stream, and then heated to 150X: After maintaining for 1 hour, it was cooled to room temperature to obtain a compound powder (the compound powder of Example 1). 0. 015 g of the compound powder of Example 1 was added to a 100 ml four-necked flask containing 5Og of acetic acid, and the temperature was raised to 90 °C under nitrogen blowing of the acetic acid layer. Nitrogen blowing was stopped, and instead of 1,3-butadiene, a flow rate of 1010 ml/min was applied, and a 10% oxygen/nitrogen mixed gas was blown in with a flow rate of 25 ml/min to start the reaction. After reacting for 3 hours, the blown gas was again switched to nitrogen, cooled to room temperature, and the compound powder was filtered off. The reaction solution was analyzed by gas chromatography to give 1,4-diethoxycarbonyl-2-butene of 2.9 匪. In addition, the concentration of ruthenium dissolved in the reaction liquid was measured by Inductively Coupled Plasma Mass Spectrometry (hereinafter referred to as φ "ICP-MS"), and it was 21 ppm. Compared with Comparative Example 3 described later, it was found that the elution of ruthenium was suppressed. [Example 2] After the compound powder of Example 1 was heated to 150 ° C in a nitrogen gas stream, the gas to be passed was switched from nitrogen to hydrogen, and the temperature was raised to 400 ° C and kept at 2 hours. Thereafter, the gas to be passed was again switched to nitrogen and cooled to room temperature to obtain a compound powder (the compound powder of Example 2). The powder of the compound of Example 2 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern is shown together with the standard peak of RhsTe2 in 312XP/Invention Manual (supplement)/97-01/96135322 37 200829331

圖1。由圖1明顯可知，實施例2之化合物粉末的粉末X 射線繞射圖案與標準波峰幾乎呈一致，故實施例2之化合物粉末為金屬間化合物，且為高純度之Rh3Te2。 [實施例3] 對条顧水加入〇· 15ra〇1之氯化铑及〇· 45_〇1之硫基水杨敲並使其溶解後，再加入氫氧化鈉而將pH調整為13，藉此調製成含鍺溶液10ml。以此作為A溶液。又’對療餾水加入〇.15mm〇i之亞碲酸鈉使其溶解後，加入氯氧化鈉將pH調整為13，藉此調製成含碲溶液 l〇ml。以此作為b溶液。又’對瘵餾水加入2mmol之氫氧化硼鈉使其溶解後，加入氮氧化納將PH調整為13，藉此調製成含氫化硼鈉溶液 1 〇m 1。以此作為c溶液。其次’混合A溶液與B溶液，於此加入蒸餾水與氫氧化納而调整為pHl 3並作成總量48ml後，以充分時間進行混合’再加入C溶液，於7〇°C進行還原3小時。將藉還原所得之黑色粉末於氮環境氣體中進行過濾、水洗’於氮氣流下以9〇°c乾燥1小時後，升溫至151TC，使流通的氣體從氮切換為氫並再升溫至4〇(rc而保持2小時。再切換為氮而冷卻至室溫，得到化合物粉末（實施例 3之化合物粉末）。figure 1. As is apparent from Fig. 1, the powder X-ray diffraction pattern of the compound powder of Example 2 was almost identical to the standard peak, so that the compound powder of Example 2 was an intermetallic compound and was of high purity Rh3Te2. [Example 3] After the hydrazine hydrate of 〇·15ra〇1 and the thiosalicyloside of 〇·45_〇1 were knocked and dissolved, the pH was adjusted to 13, Thereby, 10 ml of a cerium-containing solution was prepared. Use this as the A solution. Further, after adding the sodium citrate of 〇.15 mm〇i to the hydrolyzed water to dissolve it, the pH was adjusted to 13 by adding sodium oxychloride to prepare a hydrazine-containing solution. This is used as the b solution. Further, after adding 2 mmol of sodium borohydride to the distilled water to dissolve it, the pH was adjusted to 13 by adding sodium oxynitride, thereby preparing a sodium borohydride-containing solution 1 〇m 1 . Use this as a c solution. Next, the mixture of the A solution and the B solution was mixed, and distilled water and sodium hydroxide were added thereto to adjust the pH to 3, and a total amount of 48 ml was prepared. After mixing for a sufficient period of time, the solution C was further added, and reduction was carried out at 7 ° C for 3 hours. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, and washed with water. After drying at 9 ° C for 1 hour under a nitrogen stream, the temperature was raised to 151 TC, and the circulating gas was switched from nitrogen to hydrogen and then raised to 4 Torr ( The rc was kept for 2 hours, and then switched to nitrogen and cooled to room temperature to obtain a compound powder (the compound powder of Example 3).

對實施例3之化合物粉末進行粉末X射線繞射測定。將所得之粉末X射線繞射圖案與RhlTei之標準波峰一同示於圖2。由圖2明顯可知，實施例3之化合物粉末的粉末X 312XP/發明說明書(補件)/97-01/96135322 38 200829331 幾乎呈一致，故實施例3之化合且為高純度之RhiTei。射線繞射圖案與標準波峰物粉末為金屬間化合物， [實施例4] -^了將所使用之碲酸量設為相對於蒸顧水為 1 ，其餘依與實施例！相同之條件進行化合物粉末的合成’再依與實施例2相同之條件進行熱處理，藉此得到化合物粉末（實施例4之化合物粉末）。 _對實施例4之化合物粉末進行粉末X射線繞射測定。將所得之粉末X射線繞射圖案與肋3以4之標準波峰一同示於圖3。由圖3明顯可知’實施例4之化合物粉末的粉末X 射線繞射圖案與標準波峰幾乎呈一致，故實施例4之化合物粉末為金屬間化合物，且為高純度之Rh3Te4。 [比較例1] 對蒸顧水加入0· 15mmol之氯化錄、〇· 45mmol之硫基水揚酸’再加入氫氧化鈉，使pH分別調整為3、5、9、1 〇、 _ 11、12。於任一情況下，硫基水揚酸均未溶解，無法形成目標之前驅物的Rh錯合體。 [比較例2] 對蒸餾水加入0.15mmol之氯化鍺、〇·30ππηο1之1，3-二羥基 -4-(2- nl 啶基偶氮）苯 • (1，3-dihydroxy-4-（2-pyridylazo)benzene)(簡稱 PAR : . 分子式CuHgChN3)，再加入氫氧化鈉，將pH分別調整為3、 5、9、10、11、12。於任一情況下，PAR均未溶解，無法形成目標之前驅物的Rh錯合體。 312XP/發明說明書(補件)/97-01/96135322 39 200829331 [比較例3 ] 對蒸餾水加入0· 15mmol之氯化铑及〇· 10mm〇1之碲酸使、其溶解。以此作為D溶液。 . 將80%飽水肼溶液0.2g加入至蒸餾水10g中，加熱至 8 5 C。對此緩慢滴下D溶液，再加熱2小時，進行還原。將藉還原所得之黑色粉末於氮環境氣體中進行過濾、水洗，於氣氣下以9 0 C加熱1小時並乾燥。升溫至15〇 °C並保持1小時後，冷卻至室溫，得到化合物粉末（比較響例3之化合物粉末）。將比較例3之化合物粉末〇· 〇 15g添加至已裝有5〇g醋酸之100ml四口燒瓶中，於對醋酸層進行氮吹入之下升溫至90°C。停止氮吹入，代替其分別將丨，3-丁二烯依每1 分鐘10ml之流量，將1〇%氧/氮混合氣體依每〗分鐘25ml 之流置吹入’使反應開始。反應3小時後，將吹入氣體再认切換為氮’冷卻至室溫’過濾、出合金粉末。以I Cp—MS 籲測定溶解於反應液中之铑的濃度，結果為6〇ppm。 [比較例4 ] 將比較例3之化合物粉末於氮氣流中升溫至15 〇 t後，使流通之氣體從氮切換為氫，再升溫至400°C並保持2小時，藉此進行熱處理。其後，使流通的氣體再切換為氮而 • 冷卻至室溫，得到化合物粉末（比較例4之化合物粉末）。、對比較例4之合金粉末進行粉末X射線繞射測定。將所得之粉末X射線繞射圖案與RhsTe2之標準波峰一同示於圖 1。由圖1明顯可知，比較例4之化合物粉末的粉末X射 312XP/發明說明書(補件)/97-01/96135322 40 200829331 線繞射圖案係不同於實施例2，與標準波峰不—致 [比較例5] - 除了將所使用之碲酸量設為相對於蒎飽走炎Λ , ” Al △ 、〜苟 U· 15mm〇l -以外，其餘依與比較例3相同之條件進行化合物粉末的合成，再依與比較例4相同之條件進行熱處理，藉此得到二合物粉末（比較例5之化合物粉末）。 f 對比較例5之化合物粉末進行粉末乂射線繞射測定。將所得之粉末X射線繞射圖案與RhlTei之標準波峰—同示於圖2。由圖2明顯可知，比較例5之化合物粉末的粉Ιχ 射線繞射圖案係與實施例3不同，除了 RhlTei之標準波峰以外’亦混有認為是雜質的波峰。 [比較例6 ] 除了將所使用之碲酸量設為相對於蒸餾水為〇.2〇mm〇l 以外，其餘依與比較例3相同之條件進行化合物粉末的合成，再依與比較例4相同之條件進行熱處理，藉此得到化馨合物粉末（比較例6之化合物粉末）。對比較例6之化合物粉末進行粉末X射線繞射測定。將所得之粉末X射線繞射圖案與肋3164之標準波峰一同示於圖3。由圖3明顯可知，比較例β之合金粉末的粉末X射線繞射圖案係與實施例4不同，除了 RhsTe4之標準波峰以 * 外，亦混有認為是雜質的波峰。、[實施例5 ] 對蒸餾水加入〇.97mol之氯化铑及2.92mmol之硫基水揚酸並使其溶解後，加入氫氧化鈉而將pH調整為13，藉 41 312XP/發明說明書(補件)/97·〇ι/96135322 200829331 此5周製成含鍺溶液1 〇ml。以此作為£溶液。又，對蒸餾水加入1.94mmol之亞碲酸鈉使其溶解後， *加入氫氧化鈉將PH調整為13,藉此調製成含碲溶液 • l〇ml。以此作為F溶液。又尸，瘵餾水加入68· 〇则之氫化硼鈉使其溶解後，加入氳氧化鈉使pH調整為13，藉此調製成含氫化硼鈉溶液10ml。以此作為〇溶液。 •於顆粒成形碳⑽m公司製2x)40g中加入蒸鶴水6〇g =60%硝:酸60g’於_進行熱處理3小時後，冷卻至室乂又知水進行水洗。再於氮氣流中，依9〇充3小時、再依15(TC2小時進行乾燥處理。以處理後之活性碳作為載體Η。將Ε溶液lml與F溶液〇. 5ml混合，依充分時間予以混合後，將該混合溶液冷卻至〇ΐ。對此加入G溶液〇· 5mi，再加入2. 〇g之載體η使溶液含浸，加熱至阶進行還原魯i彳後冷卻至至溫。將所得之含有錄及碲的活性碳移 f燒成管中’於氮氣流中依9(rc3小時、再依15代2小時進行乾燥處理，得到於由活性碳組成之載體上載持了錢 —碲金屬間化合物粒子的氧化觸媒(實施例5之氧化觸媒）。 ^將貝鉍例5之氧化觸媒以穿透型電子顯微鏡進行觀 -^將所得之實施例5之氧化觸媒的穿透型電子顯微鏡照 (圖式代用照片)示於圖4。由圖4的照片可知，活性碳载體上之錄-碲金屬間化合物粒子&㈣舰之粒子徑，並 312XP/發明說明書(補件)/97-01/96135322 200829331 以高分散而被载持著。 (產業上之可利用性） ^ 本發明之铑-碲金屬間化合从” t σ物粒子，可例如廣泛地使用 •於乳化反應用之觸媒（氧化觸媒）等。又’本發明之氧化觸媒係例如藉由將氧親核劑予以氧化性加成至稀烴或芳香族化合物中，而可使用於製造氧化性加成生成物之方法（氧化性加成生成物之製造方法等）中。以上，雖使用了特定態樣詳細說明本發明，但本領域從業者當知，在不脫離本發明意圖與範圍内，可進行夂種變更。 σ 又’本申請案係根據2006年9月25曰所申請之日本專利申請（特願2006-258836)，引用其全體而援用於此。【圖式簡單說明】圖1為將實施例2及比較例4之化合物粉末的粉末X射線繞射圖案，與RhsTe2之標準波峰一同表示的圖。 φ 圖2為將貫施例3及比較例5之化合物粉末的粉末X射線繞射圖案，與RhiTei之標準波峰一同表示的圖。圖3為將實施例4及比較例6之化合物粉末的粉末X射線繞射圖案，與RhsTe4之標準波峰一同表示的圖。圖4為實施例5之氧化觸媒之穿透型電子顯微鏡照片 .(圖式取代用照片）。 312XP/發明說明書(補件)/97-〇1/96135322 43The powder of the compound of Example 3 was subjected to powder X-ray diffraction measurement. The resulting powder X-ray diffraction pattern is shown in Fig. 2 together with the standard peak of RhlTei. As is apparent from Fig. 2, the powder of the compound of Example 3, powder X 312XP / invention specification (supplement) / 97-01/96135322 38 200829331, is almost identical, so that the compound of Example 3 is a high purity RhiTei. The ray diffraction pattern and the standard peak powder are intermetallic compounds, [Example 4] - The amount of citric acid used is set to 1 with respect to the steaming water, and the rest depends on the examples! The synthesis of the compound powder was carried out under the same conditions, and heat treatment was carried out under the same conditions as in Example 2 to obtain a compound powder (the compound powder of Example 4). The powder of the compound of Example 4 was subjected to powder X-ray diffraction measurement. The resulting powder X-ray diffraction pattern is shown in Fig. 3 together with the rib 3 at a standard peak of 4. As is apparent from Fig. 3, the powder X-ray diffraction pattern of the compound powder of Example 4 was almost identical to the standard peak, so that the compound powder of Example 4 was an intermetallic compound and was of high purity Rh3Te4. [Comparative Example 1] To the steamed water, 0. 15 mmol of chlorinated chloride, 〇·45 mmol of thiosalicylic acid was added, and then sodium hydroxide was added to adjust the pH to 3, 5, 9, 1 and _, respectively. , 12. In either case, the sulfur-based salicylic acid was not dissolved, and the Rh complex of the target precursor was not formed. [Comparative Example 2] To a distilled water, 0.15 mmol of ruthenium chloride and 1,3-30ππηο1 of 1,3-dihydroxy-4-(2-nl-pyridylazo)benzene (1,3-dihydroxy-4-(2) was added. -pyridylazo)benzene) (abbreviated as PAR: . molecular formula CuHgChN3), and then added sodium hydroxide to adjust the pH to 3, 5, 9, 10, 11, and 12, respectively. In either case, the PAR did not dissolve and could not form the Rh complex of the target precursor. 312XP/Invention Manual (Supplement)/97-01/96135322 39 200829331 [Comparative Example 3] To a distilled water, 0·15 mmol of cerium chloride and cerium·10 mm 〇1 of citric acid were added and dissolved. Use this as the D solution. 0.2 g of an 80% saturated hydrazine solution was added to 10 g of distilled water and heated to 85 C. The D solution was slowly dropped on this, and heated for further 2 hours to carry out reduction. The black powder obtained by the reduction was filtered in a nitrogen atmosphere, washed with water, and heated at 90 ° C for 1 hour under air atmosphere and dried. After raising the temperature to 15 ° C for 1 hour, it was cooled to room temperature to obtain a compound powder (Comparative Compound Powder of Example 3). 15 g of the compound powder of Comparative Example 3 was added to a 100 ml four-necked flask containing 5 liters of vinegar, and the temperature was raised to 90 ° C under nitrogen blowing of the acetic acid layer. Nitrogen blowing was stopped, instead of argon, 3-butadiene, respectively, at a flow rate of 10 ml per minute, and a 1% oxygen/nitrogen mixed gas was blown in a flow of 25 ml per minute to start the reaction. After the reaction for 3 hours, the blowing gas was changed to nitrogen and cooled to room temperature to filter and release the alloy powder. The concentration of hydrazine dissolved in the reaction liquid was measured by I Cp-MS and found to be 6 〇 ppm. [Comparative Example 4] After the compound powder of Comparative Example 3 was heated to 15 Torr in a nitrogen stream, the gas to be circulated was switched from nitrogen to hydrogen, and the temperature was raised to 400 ° C for 2 hours to carry out heat treatment. Thereafter, the gas to be circulated was switched to nitrogen again. • The mixture was cooled to room temperature to obtain a compound powder (the compound powder of Comparative Example 4). The alloy powder of Comparative Example 4 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern is shown in Fig. 1 together with the standard peak of RhsTe2. As is apparent from Fig. 1, the powder X-ray 312XP/invention specification (supplement)/97-01/96135322 40 200829331 of the compound powder of Comparative Example 4 is different from that of the embodiment 2, and is not related to the standard peak [ Comparative Example 5] - The compound powder was subjected to the same conditions as in Comparative Example 3 except that the amount of citric acid used was set to be the same as that of Comparative Example 3 except for "A △ , 苟 U · 15 mm 〇 l - The resultant was subjected to heat treatment under the same conditions as in Comparative Example 4, whereby a dimer powder (the compound powder of Comparative Example 5) was obtained. f The powder of the compound of Comparative Example 5 was subjected to powder enthalpy diffraction measurement. The X-ray diffraction pattern and the standard peak of RhlTei are shown in Fig. 2. It is apparent from Fig. 2 that the powder ray diffraction pattern of the compound powder of Comparative Example 5 is different from that of Example 3 except for the standard peak of RhlTei' A peak which is considered to be an impurity is also mixed. [Comparative Example 6] The compound powder was subjected to the same conditions as in Comparative Example 3 except that the amount of citric acid used was changed to 〇.2〇mm〇l with respect to distilled water. Synthetic The heat treatment was carried out under the same conditions as in Comparative Example 4, whereby a clarified conjugate powder (the compound powder of Comparative Example 6) was obtained. The powder of the compound of Comparative Example 6 was subjected to powder X-ray diffraction measurement. The obtained powder X-ray diffraction pattern was obtained. It is shown in Fig. 3 together with the standard peak of the rib 3164. It is apparent from Fig. 3 that the powder X-ray diffraction pattern of the alloy powder of Comparative Example β is different from that of Example 4 except that the standard peak of RhsTe4 is mixed with * It is considered to be a peak of impurities. [Example 5] After adding 0.97 mol of cerium chloride and 2.92 mmol of thiohydric salicylic acid to distilled water and dissolving it, sodium hydroxide was added to adjust the pH to 13, by 41 312XP/Inventive Manual (Replenishment)/97·〇ι/96135322 200829331 This is a 5 锗 solution containing 锗 solution for 5 weeks. This is used as a solution. In addition, after adding 1.94 mmol of sodium citrate to distilled water to dissolve it, * Adding sodium hydroxide to adjust the pH to 13, thereby preparing a cerium-containing solution • l 〇 ml. This is used as the F solution. The corpse and the hydrazine water are added to the hydride of sodium hydride, and then dissolved. Sodium oxide adjusts the pH to 13, thereby modulating it into 10 ml of sodium borohydride solution was used as a bismuth solution. • Add 4 parts of steamed water to 6 g of granule-formed carbon (10)m company, 6 〇g = 60% of nitrate: 60 g of acid was heat-treated for 3 hours, and then cooled to room.乂乂知乂乂乂乂 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 After mixing and mixing for a sufficient period of time, the mixed solution was cooled to hydrazine. To this end, G solution 〇·5mi was added, and then the carrier η of 〇g was added to impregnate the solution, and the mixture was heated to a stage for reduction, and then cooled to a temperature. The obtained activated carbon containing ruthenium and ruthenium was transferred to a tube for sintering in a nitrogen stream according to 9 (rc 3 hours, followed by drying for 15 hours and 2 hours, and the obtained carrier was supported by activated carbon). Oxidation catalyst of ruthenium intermetallic compound particles (oxidation catalyst of Example 5) ^Oxidation catalyst of Bellows Example 5 was observed by a transmission electron microscope - The obtained oxidation catalyst of Example 5 was obtained. A penetrating electron microscope photograph (photograph of a substitute image) is shown in Fig. 4. From the photograph of Fig. 4, the particle diameter of the ruthenium-iridium intermetallic compound particle on the activated carbon carrier and (4) ship, and 312XP/invention specification (Supplement) /97-01/96135322 200829331 is carried with high dispersion. (Industrial Applicability) ^ The 铑-碲 intermetallic compound of the present invention can be widely used, for example, from "t σ particles". • a catalyst (oxidation catalyst) for emulsification reaction, etc. Further, the oxidation catalyst of the present invention can be used, for example, by oxidatively adding an oxygen nucleophile to a rare hydrocarbon or an aromatic compound. Method for producing an oxidative addition product (manufactured by an oxidative addition product) In the above, the present invention will be described in detail with reference to the specific embodiments thereof, and it is understood by those skilled in the art that the invention can be modified without departing from the spirit and scope of the invention. According to Japanese Patent Application No. 2006-258836 filed on Sep. 25, 2006, the entire disclosure of which is incorporated herein by reference in its entirety. A powder X-ray diffraction pattern, which is shown together with a standard peak of RhsTe2. φ Fig. 2 is a diagram showing a powder X-ray diffraction pattern of the compound powder of Example 3 and Comparative Example 5 together with a standard peak of RhiTei. Fig. 3 is a view showing a powder X-ray diffraction pattern of the compound powder of Example 4 and Comparative Example 6 together with a standard peak of RhsTe4. Fig. 4 is a transmission electron micrograph of the oxidation catalyst of Example 5. (Photograph replaced by photo) 312XP/Invention Manual (supplement)/97-〇1/96135322 43

Claims

200829331 十、申請專利範園： 1. 一種鍺-碲金屬間化合物間化合物的粒子，其特徵為，係j有錄及碲之金屬粒子徑為6〜16nm ; 姥與碲之原子比為3: 2〜3: 4。利範圍第1項之姥，金屬間化合物粒子， %中=與碲之原子比為3:2、3:4及1:1之任一者。之姥-蹄：：觸媒，其特徵為將申請專利範圍第1或2項 .^間化合物粒子載持於載體上而成。、應用:::專利範圍第3項之氧化觸媒’其為醯氧基化反 5種姥—碲金屬間化合物粒子之製造方法，盆特徵劑接觸Γ步備驟將含㈣鹽及碲鹽以及錯合劑之溶液與還原上=合劑為含有硫原子及/或氮原子之有機化合物。製造Π請2範圍第5項…金屬間化合物粒子之 '八中’使上述鍺鹽及碲鹽以及錯合劑溶解於^ 性水溶液後，再與還原劑接觸。解於鹼 7·如申請專利範圍第5項之姥_碡金屬間化合物粒子之製造方法’其中’上述錄鹽為氯化铑。制8生如申請專利範圍帛5㉟之錄一碲金屬間化合物粒子之衣以方法，其中，上述碲鹽係從由碲酸及其鹽類以及亞碲酸及其鹽類所組成群選出。 9·種鍺—碲金屬間化合物粒子，其特徵為藉由申請專 312XP/發明說明書(補件)/97-01/96135322 44 200829331 利範圍第5項之製造方法所獲得β 10.-種氧化觸媒，其特徵為將申請專利範圍第9項之 •鍺-碲金屬間化合物粒子载持於載體上而成。 .η’種氧化性加成生成物之製造方法，其特徵為，在申請專利範圍第10項之氧化觸媒及分子狀氧的存在下，使氧親核劑氧化性地加成至烯烴或芳香族化合物。200829331 X. Patent application garden: 1. A particle of a ruthenium-iridium intermetallic compound, characterized in that the metal particle diameter of the j and 碲 is 6~16nm; the atomic ratio of 姥 to 碲 is 3: 2~3: 4. In the first item of the range, the intermetallic compound particles, the ratio of % in the atom to the atom of 碲 are 3:2, 3:4 and 1:1.姥-hoof:: Catalyst, which is characterized in that the first or second item of the patent application is carried on the carrier. Application::: Oxidation catalyst of the third item of the patent range' is a method for producing 醯oxylated anti-5 kinds of ruthenium-iridium intermetallic compound particles, and the contact agent of the pot characterization agent will contain (4) salt and strontium salt. And the solution of the wronging agent and the reducing agent = the organic compound containing a sulfur atom and/or a nitrogen atom. In the fifth item of the range of the application 2, the 'eight in the intermetallic compound particles' is dissolved in the aqueous solution and then contacted with the reducing agent. Solution to the base 7. The method for producing 碡_碡 intermetallic compound particles according to item 5 of the patent application scope wherein the above-mentioned salt is ruthenium chloride. A method of coating an intermetallic compound particle as described in the patent application pp. 535, wherein the above-mentioned onium salt is selected from the group consisting of citric acid and a salt thereof, and a hydrazine acid and a salt thereof. 9. A bismuth-tellurium intermetallic compound particle characterized by a β 10.-oxidation obtained by the manufacturing method of the 312XP/invention specification (supplement)/97-01/96135322 44 200829331 The catalyst is characterized in that the 锗-碲 intermetallic compound particles of the ninth application patent range are carried on a carrier. A method for producing an oxidative addition product of η', characterized in that an oxygen nucleophile is oxidatively added to an olefin or in the presence of an oxidation catalyst and molecular oxygen of claim 10 Aromatic compound.

312ΧΡ/發明說明書(補件)/97-01/96135322 45312ΧΡ/Invention Manual (supplement)/97-01/96135322 45