JP4085566B2 - Method for producing allyl compounds - Google Patents

Description

【００１１】
上記式（ａ）及び（ｂ）において、Ｒはアセトキシル基又は水酸基であり、Ｒ¹〜Ｒ⁵は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数３〜２０のシクロアルキル基、炭素数２〜４０のジアルキルアミノ基、炭素数６〜２０のアリール基、炭素数６〜２０のアリーロキシ基、炭素数６〜２０のアルキルアリール基、炭素数６〜２０のアルキルアリーロキシ基、炭素数６〜２０のアリールアルコキシ基、シアノ基、炭素数２〜２０のエステル基、ヒドロキシ基、又はハロゲン原子を表し、置換基を有していてもよい基である。Ｒ¹〜Ｒ⁵が有していてもよい置換基としては、炭素数１〜１０のアルコシキ基、カルボキシル基、ヒドロキシル基、炭素数６〜１０のアリール基等が挙げられる。
【００１２】
上述した式（ａ）の中では、式（ａ’）：ＣＨ₂＝ＣＨ-ＣＨＲ⁶-ＣＨ₂Ｒ⁷で表される3,4-二置換ブテン-1（但し、Ｒ⁶及びＲ⁷はアセトキシル基又は水酸基である。）が好ましく、また、上述した式（ｂ）の中では、式（ｂ’）：ＣＨ₂Ｒ⁸-ＣＨ＝ＣＨ-ＣＨ₂Ｒ⁹で表される1,4-二置換ブテン-2（但し、Ｒ⁸及びＲ⁹はアセトキシル基又は水酸基である。）が好ましい。
式（ａ’）の３，４−二置換ブテン−１としては、具体的には3,4-ジアセトキシブテン-1、3-ブテン-1,2-ジオールモノアセトキシレート、3,4-ジヒドロキシブテン-1が挙げられ、また、式（ｂ’）の１，４−ジ置換ブテン−２としては、1,4-ジアセトキシブテン-2、1-アセトキシ-4-ヒドロキシ-2-ブテン、1,4-ジヒドロキシブテン-2が挙げられる。
【００１３】
また、原料の１例である３，４−ジアセトキシブテン−１は、公知の方法、例えばブタジエンをパラジウム等の触媒の存在下、酢酸及び酸素と反応させて１，４−ジアセトキシブテン−２を製造する際の副生物として得られるものであり、例えば（特公昭５１−２３００８号公報又は同５９−２８５５３号公報）に準拠して製造することができる。
原料は純品でもよいが、複数のアリル化合物の混合物であってもよく、原料のアリル化合物以外に、後述するようなこの異性化反応を妨げない他の成分、例えば、酢酸、水等を含む混合物であってもよい。
【００１４】
本発明の反応に用いられる異性化触媒は、周期表の第８〜１０族（IUPAC 無機化学命名法改訂版（1989））の金属の化合物を含むものである。金属化合物としては、例えば鉄、コバルト、ニッケル、ルテニウム、ロジウム、白金、イリジウム、オスミウム及びパラジウムの化合物から選ばれる１種以上の化合物が挙げられるが、これらの中では、ニッケル、パラジウム、白金化合物がより好ましく、更にはパラジウム化合物が特に好ましい。
前記金属化合物は、例えば、酢酸塩、アセチルアセトナート、ハライド、硫酸塩、硝酸塩、有機塩、無機塩、アルケン化合物、アミン化合物、ピリジン化合物、ホスフィン配位化合物、ホスファイト配位化合物等が挙げられる。
【００１５】
ルテニウム化合物としては、ＲｕＣｌ₃、Ｒｕ（ＯＡｃ）₃、Ｒｕ（ａｃａｃ）₃、ＲｕＣｌ₂（ＰＰｈ₃）₃等が挙げられ、オスミウム化合物としては、ＯｓＣｌ₃、Ｏｓ（ＯＡｃ）₃等が挙げられ、ロジウム化合物としては、ＲｈＣｌ₃、Ｒｈ（ＯＡｃ）₃、ロジウムジアセテート二量体、Ｒｈ（acac）(CO)₂、［Ｒｈ（ＯＡｃ）（ＣＯＤ）］₂、［ＲｈＣｌ（ＣＯＤ）］₂、Ｒｈ（ＣＯＤ）ＯＡｃなどが挙げられる。
また、イリジウム化合物としては、ＩｒＣｌ₃、Ｉｒ（ＯＡｃ）₃等が挙げられ、ニッケル化合物としては、ＮｉＣｌ₂、ＮｉＢｒ₂、Ｎｉ（ＮＯ₃）₂、ＮｉＳＯ₄、Ｎｉ（ＣＯＤ）₂、ＮｉＣｌ₂（ＰＰｈ₃）₂等が挙げられる。
【００１６】
パラジウム化合物としては、例えば、Ｐｄ（０）やＰｄＣｌ₂ 、ＰｄＢｒ₂ 、ＰｄＣｌ₂ （ＣＯＤ）、ＰｄＣｌ₂ （ＰＰｈ₃ ）₂ 、Ｐｄ（ＰＰｈ₃）₄、Ｐｄ₂（ｄｂａ）₃・ＣＨＣｌ₃、Ｋ₂ＰｄＣｌ₄、Ｋ₂ＰｄＣｌ₆（potassium hexachloropalladate(IV))、ＰｄＣｌ₂（ＰｈＣＮ）₂、ＰｄＣｌ₂（ＣＨ₃ＣＮ）₂、、Ｐｄ（ｄｂａ）₂、Ｐｄ2（ｄｂａ）₃、Ｐｄ（ＮＯ₃ ）₂ 、Ｐｄ（ＯＡｃ）₂ 、Ｐｄ（ＣＦ₃ＣＯＯ）₂、ＰｄＳＯ₄、Ｐｄ（ａｃａｃ）₂ 、カルボキシレート化合物、オレフィン含有化合物、Ｐｄ（ＰＰｈ₃）₄等の有機ホスフィン含有化合物、アリルパラジウムクロライド二量体等を挙げることができ、これらの中、Ｐｄ（ＯＡｃ）₂ 、ＰｄＣｌ₂ 等のパラジウムのカルボキシレート化合物又はハロゲン化物が好ましい。
白金化合物としては、Ｐｔ（ａｃａｃ）₂、ＰｔＣｌ₂（ＣＯＤ）、ＰｔＣｌ₂（ＣＨ₃ＣＮ）₂、ＰｔＣｌ₂（ＰｈＣＮ）₂、Ｐｔ（ＰＰｈ₃）₄、Ｋ₂ＰｔＣｌ₄、Ｎａ₂ＰｔＣｌ₆、Ｈ₂ＰｔＣｌ₆等が挙げられる。（ここで、ＣＯＤ：シクロペンタジエン、ｄｂａ：ジベンジリデンアセトン、acac：アセチルアセトナートを表す。）
本発明においては、上述した金属化合物の形態には特に制限されず、活性な金属錯体種は単量体、二量体及び／又は多量体であってもかまわない。
【００１７】
これらの金属化合物の使用量については特に制限はないが、触媒活性と経済性の観点から、反応原料であるアリル化合物に対して１×１０^-8（０．０１モルｐｐｍ）〜１モル当量、好ましくは１×１０^-7（０．１モルｐｐｍ）〜０．００１モル当量の範囲、特に好ましくは１０^-6〜０．０００１モル等量の範囲で使用される。
【００１８】
本発明においては、上述した特定の金属化合物を含む触媒を用いる異性化反応系中に、カルボン酸、例えば炭素数２〜８の脂肪酸や炭素数６〜１２の芳香族カルボン酸を存在させることにより、異性化反応を促進するという利点を有する。中でも、酢酸、プロピオン酸、酪酸等の炭素数２〜６の脂肪酸が好ましく、酢酸が最も好ましい。カルボン酸の存在量は、触媒活性、触媒の安定性及び経済性の観点から、酢酸：原料であるアリル原料化合物の合計量（重量比）で、通常１０：１〜１：１０００であり、好ましくは、４：１〜１：１００、更に好ましくは２：１〜１：２０の範囲内である。
本発明では、異性化反応のアリール原料化合物が、置換基としてカルボキシル基を有する場合であっても、別途、カルボン酸を存在させる必要がある。
【００１９】
本発明においては、上述した金属化合物と共に有機リン化合物を触媒成分として用いることが好ましい。有機リン化合物としては、単座又は多座のホスフィン類、ホスファイト類、ホスホナイト類、ホスフィナイト類等が挙げられるが、中でもホスファイト化合物が好ましい。ホスファイト化合物については、特に限定はされないが、好ましいホスファイト化合物は、下記一般式（Ｉ）、（II）、（III)、（IV）、（Ｖ）及び（VI）で示される化合物の中の少なくとも一種である。
【００２０】
【化３】

【００２１】
式（Ｉ）〜（VI）において、Ｒ¹⁰〜Ｒ²¹は、それぞれ独立して、アルキル基、アルコキシ基、シクロアルキル基、アリーロキシ基、アルキルアリーロキシ基、アリールアルコキシ基、又はアリール基を表し、更に置換基を有していてもよい。
【００２２】
Ｒ¹⁰〜Ｒ²¹としてアルキル基を用いる場合、又は、アルキル骨格を有する置換基（アルキルアリーロキシ基中のアルキル基等）を用いる場合には、その炭素数は通常１〜２０であり、好ましくは１〜１４である。その具体例としては、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ヘキシル基、オクチル基、デシル基等である。また、アルキル基又はアルキル骨格部分は更に置換基を有していてもよく、置換基としては、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、アミノ基、シアノ基、炭素数２〜１０のエステル基、ヒドロキシ基及びハロゲン原子が挙げられる。
【００２３】
また、Ｒ¹⁰〜Ｒ²¹としてアリール基を用いる場合又はアリール骨格を有する置換基を用いる場合には、その炭素数は通常６〜２０であり、好ましくは６〜１４である。具体例としては、フェニル基、トリル基、キシリル基、ジ−ｔ−ブチルフェニル基、ナフチル基、ジ−ｔ−ブチルナフチル基等が挙げられる。
アリール基又はアリール骨格部分は更に置換基を有していてもよく、置換基としては、水素原子、炭素数１〜２０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数６〜２０のアリーロキシ基、炭素数６〜２０のアルキルアリール基、炭素数６〜２０のアルキルアリーロキシ基、炭素数６〜２０のアリールアルキル基、炭素数６〜２０のアリールアルコキシ基、シアノ基、炭素数２〜２０のエステル基、ヒドロキシ基及びハロゲン原子が挙げられる。
【００２４】
Ｒ¹⁰〜Ｒ²¹の具体例としては、フェニル基、2-メチルフェニル基、3-メチルフェニル基、4-メチルフェニル基、2,3-ジメチルフェニル基、2,4-ジメチルフェニル基、2,5-ジメチルフェニル基、2,6-ジメチルフェニル基、2-エチルフェニル基、2-イソプロピルフェニル基、2-t-ブチルフェニル基、2,4-ジ-t-ブチルフェニル基、2-クロロフェニル基、3-クロロフェニル基、4-クロロフェニル基、2,3-ジクロロフェニル基、2,4-ジクロロフェニル基、2,5-ジクロロフェニル基、3,4-ジクロロフェニル基、3,5-ジクロロフェニル基、4-トリフルオロメチルフェニル基、2-メトキシフェニル基、3-メトキシフェニル基、4-メトキシフェニル基、3,5-ジメトキシフェニル基、4-シアノフェニル基、4-ニトロフェニル基、トリフルオロメチル基、ペンタフルオロエチル基、ペンタフルオロフェニル基、及び下記の（C-1）〜（C-8）が挙げられる。
【００２５】
【化４】

【００２６】
Ｚ¹〜Ｚ⁴及びＡ¹〜Ａ³は、それぞれ独立して、置換基を有していてもよい炭素数１〜２０のアルキレン基、置換基を有してもよい炭素数６〜３０のアリーレン基、又は−Ａｒ¹ −（Ｑ¹）_n −Ａｒ²−なる真中に二価の連結基を有してもよいジアリーレン基（但し、Ａｒ¹ 及びＡｒ² は、それぞれ独立して、置換基を有してもよい炭素数６〜１８のアリーレン基を表す。）を表す。Ｔは、炭素原子、アルカンテトライル基、ベンゼンテトライル基、又はＴ²-（Ｑ²）_n-Ｔ²で表される置換基を有していてもよい四価の基であり、Ｔ¹及びＴ²は、それぞれ独立して、炭素数１〜１０のアルカントリイル基及び炭素数６〜１５のベンゼントリイル基から選ばれる置換基を有していてもよい三価の有機基を表す。Ｑ¹及びＱ²は、それぞれ独立して、−ＣＲ²²Ｒ²³−、−Ｏ−、−Ｓ−又は−ＣＯ−を表し、ｎは０又は１であり、Ｒ²²及びＲ²³は、それぞれ独立して水素原子、炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基であり、置換基を有していてもよい。
【００２７】
また、Ｚ¹〜Ｚ⁴又はＡ¹〜Ａ³がアルキレン基の場合、その具体例としては、例えばテトラメチルエチレン基、ジメチルプロピレン基等が挙げられ、Ｚが置換基を有してもよいアルキレン基の場合には、置換基としては炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、アミノ基、シアノ基、アミド基、ニトロ基、トリフルオロメチル基、トリメチルシリル基、炭素数３〜１０のエステル基、ヒドロキシ基及びハロゲン原子が挙げられる。
また、Ｚ¹〜Ｚ⁴又はＡ¹〜Ａ³が置換基を有していてもよいアリーレン基の場合には、その具体例としては、例えばフェニレン基やナフチレン基等が挙げられ、置換基としては、炭素数１〜８のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、アミノ基、シアノ基、炭素数２〜１０のエステル基、アミド基、ニトロ基、トリフルオロメチル基、トリメチルシリル基、ヒドロキシ基及びハロゲン原子等が挙げられる。
更に、Ｚ¹〜Ｚ⁴又はＡ¹〜Ａ³が−Ａｒ¹ −（Ｑ）_n −Ａｒ² −なる真中に二価の連結基を有してもよいジアリーレン基の場合、Ａｒ¹ 及びＡｒ² は置換基を有してもよいアリーレン基であり、その炭素数は６〜２４、更には６〜１６が好ましく、置換基の好ましい具体例としては炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１０のアリール基、アミノ基、シアノ基、炭素数２〜１０のエステル基、ヒドロキシ基及びハロゲン原子等が挙げられる。
また、Ａ¹〜Ａ³及びＺ¹〜Ｚ⁴の具体例としては、−（ＣＨ₂ ）₂ −、−（ＣＨ₂ ）₃ −、−（ＣＨ₂ ）₄ −、−（ＣＨ₂ ）₅ −、−（ＣＨ₂ ）₆ −、−ＣＨ（ＣＨ₃ ）−ＣＨ（ＣＨ₃ ）−、−ＣＨ（ＣＨ₃ ）ＣＨ₂ ＣＨ（ＣＨ₃ ）−、−Ｃ（ＣＨ₃ ）₂ −Ｃ（ＣＨ₃ ）₂ −、−Ｃ（ＣＨ₃ ）₂ −ＣＨ₂−Ｃ（ＣＨ₃ ）₂ −、及び下記の（Ａ−１）〜（Ａ−４６）が挙げられる。また、Ａ1〜Ａ3の具体例としては（Ａ−４７）も挙げられる。
【００２８】
【化５】

【００２９】
【化６】

【００３０】
【化７】

【００３１】
【化８】

【００３２】
【化９】

【００３３】
【化１０】

【００３４】
そして、式（Ｉ）〜（VI）の化合物の好ましい具体例として、下記の（１）〜（１２）及び（Ｐ１）〜（Ｐ２１）を例示することができる。
【００３５】
【化１１】

【００３６】
【化１２】

【００３７】
【化１３】

【００３８】
【化１４】

【００３９】
【化１５】

【００４０】
【化１６】

【００４１】
ホスフィン類の具体例としては、トリフェニルホスフィン、トリ（ノルマルブチル）ホスフィン、トリ（ｔ−ブチル）ホスフィン、ジフェニルホスフィノエタン、ジフェニルホスフィノメタン、ジフェニルホスフィノプロパン、ジフェニルホスフィノブタンや下記の（１３）〜（２０）を例示することができる。
【００４２】
【化１７】

【００４３】
また、ホスホナイト類、ホスフィナイト類としては、下記の（２１）〜（３５）を例示することができる。
【００４４】
【化１８】

【００４５】
【化１９】

【００４６】
【化２０】

【００４７】
異性化反応系内における、これらの有機リン化合物の上記金属化合物に対する比率（モル比）は、通常０．１〜１００００であり、好ましくは０．５〜５００、特に好ましくは１．０〜１００の範囲で使用される。上記金属化合物と有機リン化合物はそれぞれ単独に反応系に添加してもよいし、或いは予め錯化した状態で使用しても良い。
【００４８】
異性化反応は、通常は液相で行い、溶媒の存在下或いは非存在下の何れでも実施しうるが、通常は異性化反応に溶媒を使用して均一系で実施するのが好ましい。溶媒としては、触媒及び原料化合物を溶解するものであれば使用可能であり特に限定はない。
【００４９】
溶媒の具体例としては、例えば、酢酸等のカルボン酸類、メタノール等のアルコール類、ジグライム、ジフェニルエーテル、ジベンジルエーテル、テトラヒドロフラン(THF)、ジオキサン等のエーテル類、Ｎ−メチルピロリドン（NMP）、ジメチルホルムアミド(DMF)、ジメチルアセトアミド等のアミド類、シクロヘキサノン等のケトン類、酢酸ブチル、γ−ブチロラクトン、ジ（n-オクチル）フタレート等のエステル類、トルエン、キシレン、ドデシルベンゼン等の芳香族炭化水素類、異性化反応系内で副生物として生成する高沸物、原料であるアリル化合物自体等が挙げられる。これらの中でも本発明で規定する酢酸等のカルボン酸を溶媒として用いるのが異性化反応を促進するという点で好ましい。
これらの溶媒の使用量は特に限定されるものではないが、通常、原料であるアリル化合物の合計量に対して０．１〜２０重量倍、好ましくは０．５〜１０重量倍である。
【００５０】
本発明においては、３，４−ジアセトキシブテン−１の異性化により１，４−ジアセトキシブテン−２を得る反応は平衡反応であり、１２０℃での平衡混合物は、約６０〜６５モル％の１，４−ジアセトキシブテン−２と３５〜４０モル％の３，４−ジアセトキシブテン−１を含有する。このことは、即ち、１，４−ジアセトキシブテン−２を主成分として含む反応混合物は、異性化反応させることにより、３，４−ジアセトキシブテン−１を主成分として含む生成物が得られることを意味している。
【００５１】
異性化反応により得られる生成物中の１，４−ジアセトキシブテン−２と３，４−ジアセトキシブテン−１のモル比の範囲は通常、９０：１０〜１０：９０であるが、その範囲内では８０：２０、７０：３０、６０：４０、５０：５０、４０：６０、３０：７０、２０：８０等のいずれの比率の生成物でも製造することができる。この比率は、特に限定されないが、反応条件やプロセスの経済性により調節することが可能となる。
【００５２】
本発明の異性化反応系中には、原料や基質以外の反応副生物や触媒の分解物等を含んでいてもよい。
具体的には、異性化反応系中に、ブタンジオールモノアセトキシレート、1-アセトキシブタン-2-オン、4-アセトキシブタナール、4-アセトキシクロトンアルデヒド、ジアセトキシブタン、アセトキシヒドロキシブタン、ブタンジオール、１，４−ブテンジオール、１，２−ブテンジオール、1-アセトキシ-1,3-ブタジエン、ジアセトキシオクタジエンから選ばれる１種以上の化合物（Ｃ）が存在していてもよい。
これらの化合物（Ｃ）は、異性化反応系内において、原料であるアリル化合物の合計量に対して（化合物（Ｃ）：アリル化合物）、重量比で、通常１：１〜１：１００００、好ましくは５：１〜１：１０００、更に好ましくは２：１〜１：５００、特に好ましくは０．１：１〜１：１００の範囲存在していてもよい。
【００５３】
本発明においては、異性化反応系中に水が多量に存在すると、異性化反応が著しく阻害されるため水の存在量は少ない方が転化率が高くなるという点で好ましいが、溶媒又は反応原料から完全に水を除外するためには、極めて大きなエネルギーを必要とする。従って、工業的には、異性化反応混合液中の水の存在量は、好ましくは０．１〜５wt％であり、更に好ましくは０．５〜２wt％である。水は反応系に様々なルートから混入しうるが、中でも溶媒又は異性化反応の促進剤として用いられるカルボン酸は、しばしば水を同伴する。このような場合、カルボン酸に対する水の重量比は、好ましくは１以下である。
【００５４】
本発明は、上述したようにブタジエンを、酢酸及び酸素の存在下にジアセトキシ化反応させて得られた1,4-ジアセトキシ-2-ブテンと3,4-ジアセトキシ-1-ブテンを含む反応生成物から、3,4-ジアセトキシ-1-ブテンを主成分とする反応液を分離して、次いで本発明の方法により異性化させることにより1,4-ジアセトキシ-2-ブテンを得るプロセスとして採用する場合にも有効である。
【００５５】
このようなブタジエンのジアセトキシ化反応により得られた反応生成物を原料として用いる場合には、反応生成物中に、1,4-ジアセトキシ-2-ブテンや3,4-ジアセトキシ-1-ブテン等のジアセトキシ体以外にも、上述した化合物（Ｃ）と同様の化合物が存在するため、更に、蒸留等の方法により、3,4-二置換-1-ブテン体又は1,4-二置換-2-ブテン体のいずれか一方の成分を主体として含有する混合物を分離し、次いでこの混合物の異性化反応を行うのが好ましい。
【００５６】
このように蒸留等の操作により分離された3,4-二置換-1-ブテン体及び／又は1,4-二置換-2-ブテン体を含有する混合物中には、ジアセトキシ体とモノアセトキシ体が含有されているが、モノアセトキシ体はジアセトキシ体に比べて異性化反応速度が非常に低い。従って、このようなジアセトキシ体とモノアセトキシ体の混合物の異性化反応を行う場合には、１）異性化反応を行う前に予めモノアセトキシ体のアセトキシ化反応（エステル化反応）を行い、次いで得られたジアセトキシ体を含む混合物の異性化反応を行う方法か、或いは２）異性化反応系中でモノアセトキシ体のアセトキシ化反応（エステル化反応）を同時に行う方法を採用するのがよい。
【００５７】
上述したモノアセトキシ体、例えば3-ブテン-1,2-ジオールモノアセトキシレート及び／又は1-アセトキシ-4-ヒドロキシ-2-ブテン等のアセトキシ化反応（エステル化反応）は、無水酢酸を存在させることにより進行する。無水酢酸の量は、特に制限されないが、モノアセトキシ体に対して等モル付近であればよい。無水酢酸を使用する場合の、エステル化反応の反応温度は、通常４０〜２００℃であり、好ましくは１００〜１６０℃である。
【００５８】
上述したモノアセトキシ体のアセトキシ化反応は、イオン交換樹脂及び酢酸を存在させることによっても進行する。イオン交換樹脂を用いることにより、高価な無水酢酸を使用することなくアセトキシ化反応を実施できるという利点を有する。酢酸の量は特に制限されないが、反応が平衡反応であるので、酢酸の量が多くなるほどアセトキシ化反応の転化率は向上する。
採用できるイオン交換樹脂の種類としては、スチレン系、メタクリル酸系、アクリル酸系等の陽イオン交換樹脂が挙げられ、中でもスチレン系陽イオン交換樹脂が好ましい。イオン交換樹脂の使用量としては、特に制限されないが、触媒活性と経済性の観点から、回分法の場合にはアリル原料化合物１ｋｇに対して、好ましくは０．０１〜５ｋｇであり、更に好ましくは０．０５〜１ｋｇであり、連続法の場合には、空間速度（ｓｐａｃｅ ｖｏｌｕｍｅ）は、アリル化合物１リットル、１時間当たり、好ましくは０．０５〜１０リットル、更に好ましくは０．２〜２リットルである。イオン交換樹脂を使用する場合の、エステル化反応温度としては、通常２０〜２００℃であり、好ましくは３０〜１２０℃、更に好ましくは４０〜１００℃である。
【００５９】
上述したような、異性化反応系中でモノアセトキシ体のアセトキシ化反応（エステル化反応）を同時に行う方法２）を採用する場合には、上記の無水酢酸やイオン交換樹脂及び酢酸を用いることにより、異性化反応とエステル化反応を同一の反応条件、即ち上述した異性化反応条件下で実施することが可能である。
【００６０】
本発明の異性化方法は、回分式、連続式の何れでも実施できる。
回分式で異性化反応を行う場合をより具体的に説明すると、触媒構成成分を溶媒に溶解し、この中に例えば３，４−ジアセトキシブテン−１を主体とする原料を導入し、攪拌下十分転化する時間触媒と接触させる。反応終了後は、蒸留等の手段により、反応液から目的の１，４−ジアセトキシブテン−２等を主体とする成分を分離、回収することができる。
１，４−ジアセトキシブテン−２と３，４−ジアセトキシブテン−１の分離は通常蒸留や抽出等の方法により行うことができる。
【００６１】
連続式で行う場合には、例えば３，４−ジアセトキシブテン−１を主体とする原料と触媒成分を連続的に反応槽に供給し、目的生成物である異性化物を含む反応液を連続的に抜き出した後蒸留し、触媒成分を含む残留液を連続的に反応系に循環して再利用する方式が考えられる。
異性化の反応温度は、通常５０〜２００℃、好ましくは８０〜１６０℃である。反応温度が低すぎると活性が低く、また、高すぎると触媒の安定性が低下し好ましくない副反応が起こる。反応圧力については、特に制限はなく、常圧〜３ＭＰａの範囲、好ましくは常圧〜２ＭＰａの範囲から適宜選択される。また、反応時間も特に制限がなく触媒の量、反応温度等の因子から反応速度を考慮して適宜選択する。
【００６２】
なお、3,4-ジ置換体の異性化により、対応する1,4-ジ置換体を得る反応は平衡反応であり、触媒は反応原料組成から平衡組成へより近づける役割をなす。つまり、出発原料が3,4-ジ置換体と1,4-ジ置換体のいずれを主体とする混合物の場合であってもその効果は同じである。従って、１，４−ジアセトキシブテン−２を主体とする成分の異性化反応については、原料として１，４−ジアセトキシブテン−２又はこれを含む混合物を用いる他は、上述した３，４−ジアセトキシブテン−１を主体とする原料の異性化反応に準じて行うことができる。
【００６３】
本発明によれば、3,4-ジ置換ブテン-1及び／又は1,4-ジ置換ブテン-2を、周期表の第８〜１０族の元素の金属化合物を含む触媒の存在下で異性化させる際、該金属化合物の析出を抑制しつつ、且つ、異性化生成物を１０モル％以上の収率で得ることが可能となる。
【００６４】
【実施例】
以下に本発明をより更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に制約されるものではない。尚、以下の例における反応結果はガスクロマトグラフィーにより反応液組成を分析した結果より算出した。
３，４−ジアセトキシブテン−１（以下、３，４−ＤＡＢＥと略記することがある）を原料にした場合、生成物として１，４−ジアセトキシブテン−２（以下、１，４−ＤＡＢＥと略記することがある）以外検出できないので、１，４−ジアセトキシブテン−２の収率をもって反応成績とした。また、ホスファイト化合物としては、前記の（Ｐ１）〜（Ｐ２１）を用い、ホスファイトを使用する全ての反応は窒素雰囲気下において実施した。
【００６５】
実施例１〜８
窒素置換した１０ｍｌのフラスコに３，４−ジアセトキシブテン−１（３，４−ＤＡＢＥ：０．６３３ｍｍｏｌ）、Ｐｄ（ＯＡｃ）₂ （０．０２２１ｍｍｏｌ）、前記ホスファイト化合物（０．０４１ｍｍｏｌ）及び酢酸（１ｍｌ：原料３，４−ＤＡＢＥに対する重量比は９．６４を加えて８０℃で１時間反応させた。１，４−ジアセトキシブテン−２（１，４−ＤＡＢＥ）の収率を表１に示した。尚、いずれの系でもＰｄ金属の析出は認められなかった。
【００６６】
【表１】

【００６７】
比較例１
実施例３で使用した酢酸の代わりにジグライム１ｍｌを使用し、反応温度を１２０℃に変更した以外実施例３と同様の反応を行った所、１，４−ＤＡＢＥの収率は５６．５％であった。この場合もパラジウム金属の析出は観測できなかった。実施例３と比較例１とを比べると、酢酸を存在させることにより、１，４−ＤＡＢＥの収率が向上することが分かる。
【００６８】
実施例９
Ｐｄ（ＯＡｃ）₂ （０．６３３ｍｍｏｌ）、ホスファイト化合物として（Ｐ３）（０．０４１ｍｍｏｌ）、酢酸（０．０３７ｍｌ；原料ＤＡＢＥに対する重量比は３．５６）、ジグライム１ｍｌ及び３，４−ジアセトキシブテン−１（３，４−ＤＡＢＥ）又は１，４−ジアセトキシブテン−２（１，４−ＤＡＢＥ）を０．６３３ｍｍｏｌ仕込み、６８℃で反応を行った結果を図１に示した。どちらの原料でもほぼ１００分程度で異性化反応が終了し、平衡濃度に達することが判明した。この場合もホスファイト化合物が存在する限りパラジウムの析出は認められなかった。
【００６９】
実施例１０〜１２（Ｐｄ系、Ｐ１９〜２１使用例）
３，４−ジアセトキシブテン−１ １ｍｌ（６．３ｍｍｏｌ）中に、Ｐｄ（ＯＡｃ）₂ ２１μｍｏｌ（５ｍｇ）と前記ホスファイト化合物（Ｐ１９）〜（Ｐ２１）各々１２ｍｇを溶解させ、次いで酢酸（１０μｌ；原料ＤＡＢＥに対する重量比は０．０９６８）を加えて１２０℃で３０分反応させた。結果を下記表２に示した。尚、いずれの系でもＰｄ金属の析出は認められなかった。
【００７０】
【表２】

【００７１】
実施例１３（Ｐｄ系、Ｐ１３使用）
Ｐｄ（ｄｂａ）2 ３．７ｍｇ（６．４μｍｏｌ）と前記ホスファイト化合物（Ｐ１３）４０ｍｇ（５１μｍｏｌ）を、３，４−ジアセトキシブテン−１１ｍｌ（６．３ｍｍｏｌ）に１２０℃で溶解させ、ついでこの溶液１０μｌを、酢酸（１ｍｌ；原料ＤＡＢＥに対する重量比は９．５９）と３，４−ジアセトキシブテン−１ １ｍｌ（６．３ｍｍｏｌ）を含む別のSchlenk tubeに加えて、１２０℃で３時間反応させた。モルバランスは９９％以上であり、反応生成液を分析したところ、１，４−ＤＡＢＥが６２％と３，４−ＤＡＢＥが３８％含まれていた。また、この反応においてＰｄ金属の析出は認められなかった。
【００７２】
実施例１４（酢酸量の影響）
下記表３に示した濃度のＰｄ（ＯＡｃ）₂とＰｄに対して４モル当量のビスホスファイト（Ｐ４）を、表３に示した量の酢酸と３，４−ＤＡＢＥ １ｍｌ（６．３ｍｍｏｌ）を含むフラスコに加えて１２０℃で１時間反応させた。結果を表３に示した。また、この反応においてＰｄ金属の析出は認められなかった。
【００７３】
【表３】

*：反応時間を１５分間とした。
^**：[ ]内の数値は原料DABEに対する酢酸の重量比を表す。
表３の結果より、酢酸の濃度が高い領域、即ちＰd化合物濃度が低い領域では、モルバランスが９８％以上と高くなることが分かる。
【００７４】
実施例１５（Ｐｔ系、ホスファイトＰ１３使用）
３，４−ジアセトキシブテン−１ １ｍｌ（６．３ｍｍｏｌ）中に、Ｐｔ（acac）₂ ２．５ｍｇ（６．２１μｍｏｌ）と前記ホスファイト化合物（Ｐ１３）１０ｍｇ（１３μｍｏｌ）を溶解させ、次いで、酢酸（１ｍｌ；原料ＤＡＢＥに対する重量比は９．６８）を加えて１２０℃で１時間反応させた。反応生成液をＧＣ分析したところ、１，４−ＤＡＢＥが１７mol％（tranc/cis=4.5）と３，４−ＤＡＢＥが８３mol％含まれていた。また、この反応においてＰｔ金属の析出は認められなかった。
【００７５】
実施例１６（Ｒｈ系、ホスファイトＰ１３使用）
３，４−ジアセトキシブテン−１ １ｍｌ（６．３ｍｍｏｌ）中に、［Ｒｈ（COD）ＯＡｃ］₂ １．８ｍｇ（３．５μｍｏｌ）と前記ホスファイト化合物（Ｐ１３）１０ｍｇ（１３μｍｏｌ）を溶解させ、次いで酢酸（１ｍｌ；原料ＤＡＢＥに対する重量比は９．６８）を加えて１２０℃で１時間反応させた。反応生成液をＧＣ分析したところ、１，４−ＤＡＢＥが６．３％（tranc/cis=4.3）と３，４−ＤＡＢＥが９２％含まれていた。また、この反応においてＲｈ金属の析出は認められなかった。
【００７６】
比較例２
窒素置換した１０ｍｌのフラスコに３，４−ジアセトキシブテン−１（０．６３３ｍｍｏｌ）、Ｐｄ（ＯＡｃ）₂ （０．０６ｍｍｏｌ）及びジグライム１ｍｌを使用し、反応温度１２０℃で１時間反応を行った所、１，４−ＤＡＢＥの収率は１．３％であった。しかしながら、反応終了後のフラスコ表面にパラジウムの金属ミラーが観測された。
【００７７】
【発明の効果】
本発明によれば、３，４−二置換ブテン−１及び／又は１，４−二置換ブテン−２等のアリル原料化合物を第８〜１０族の金属化合物を含む触媒及びカルボン酸の存在下で異性化させることにより、高転化率、高選択率で、且つ、金属の析出を抑制しつつ、対応する異性体である１，４−二置換ブテン−２及び／又は３，４−二置換ブテン−１等を製造することができる。
【図面の簡単な説明】
【図１】実施例９における３，４−ジアセトキシブテン−１及び１，４−ジアセトキシブテン−２の異性化反応速度を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for isomerizing a compound having an acyloxy group or a hydroxyl group at an allylic position by allylic rearrangement. Specifically, 3,4-disubstituted butene-1 and / or 1,4-disubstituted butene-2 is specified. To the corresponding isomers of 1,4-disubstituted butene-2 and / or 3,4-disubstituted butene-1.
1,4-diacetoxybutene-2 obtained by the method of the present invention is an important intermediate for producing 1,4-butanediol, tetrahydrofuran or the like. On the other hand, 3,4-diacetoxybutene-1 is an important intermediate for producing pharmaceuticals, agricultural chemicals, various fragrances and the like, including terpentene compounds such as vitamin A acetate.
[0002]
[Prior art]
It is known that 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 can be obtained by oxidizing butadiene with molecular oxygen in an acetic acid solvent (for example, JP-A-48-72090). Gazette, JP-A-48-96513, etc.). However, in this method, the production ratio of 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 depends mainly on the performance of the catalyst. It was difficult.
Further, 3,4-diacetoxybutene-1 can be easily obtained by acetoxylation of 1,2-epoxybutene-3, but in this method, 1,4-diacetoxybutene-2 is obtained. It was extremely difficult. On the other hand, in order to selectively produce only 1,4-diacetoxybutene-2, a very special raw material such as 3,6-dihydro-1,2-dioxyin is required. The production of was virtually impossible.
[0003]
Therefore, 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2 is isomerized using a specific catalyst, and 1,4-diacetoxybutene-2 which is a corresponding isomer, respectively. Various methods have been proposed in the past for producing 3,4-diacetoxybutene-1. For example, a method using a platinum chloride compound as a catalyst (German Patent Nos. 2,736,695 and 2,134,115), a method using a palladium compound in the presence of hydrogen chloride or hydrogen bromide (Japanese Patent Laid-Open No. 57-140744). Gazette), PdCl ₂ A method using a (PhCN) 2 compound (US Pat. No. 4,095,030) is known. However, these methods have a problem in the stability of the catalyst, and thus have a problem that a large amount of a highly corrosive halogen compound has to be used.
[0004]
Further, as a method not using a halogen compound, a method using a catalyst composed of a palladium compound and an organic phosphine (Japanese Patent Laid-Open No. 55-11555) or a method of isomerizing in a gas phase using an acid catalyst such as alumina or zeolite ( German Patent 3,326,668 and Japanese Patent Application Laid-Open No. 50-126611) have also been proposed, but the activity is not at a satisfactory level.
On the other hand, there has been proposed a method for improving the activity by allowing acetic acid to be present in the isomerization reaction system (Japanese Patent Laid-Open No. Sho 55-167253), but the effect was confirmed by using an ion exchange resin as a catalyst. Limited to the case. Moreover, the activity is low and it is not at a satisfactory level.
[0005]
[Problems to be solved by the invention]
As mentioned above, 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 are intermediates in completely different product groups, so the demand ratio is the region, the era, or the company that implements it. It depends on the business background. Accordingly, 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2 is isomerized using a specific catalyst, and 1,4-diacetoxybutene-2 which is the corresponding isomer, respectively. And / or 3,4-diacetoxybutene-1 is very important for industrial production, but in the conventional method, the activity of the catalyst is not at a satisfactory level, or the selectivity is not sufficient. It was not satisfactory from the industrial point of view.
[0006]
In general, metal catalysts such as PdCl ₂ When the allyl raw material compound is π-coordinated to Pd, the functional group in the allylic position (for example, an acetoxy group) is coordinated to Pd, and when it is eliminated together with the allyl raw material compound. It is believed that isomerization proceeds. Therefore, when a metal compound is used as a catalyst, unlike the case where a cation exchange resin is used as a catalyst, the presence of a carboxylic acid in a reaction solution is generally not considered to promote the reaction.
However, as a result of intensive studies by the present inventors, surprisingly, when an isomerization reaction is carried out using a catalyst containing a metal compound of Groups 8 to 10 of the periodic table, It has been found that the reaction is significantly accelerated in the presence of carboxylic acid.
Accordingly, an object of the present invention is to use a group 8-10 metal compound of the periodic table as a catalyst, and use an allyl compound such as 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2. Isomerization of the desired 1,4-diacetoxybutene-2 and / or 3,4-diacetoxybutene-1 without high metal conversion and high metal selectivity. It is in providing the method of manufacturing allyl compounds, such as.
[0007]
[Means for Solving the Problems]
As a result of intensive studies in view of such circumstances, the present inventors have found that when an allylic raw material compound is isomerized by allylic rearrangement in the presence of a catalyst containing a metal compound of Groups 8 to 10 of the periodic table, a carboxylic acid is used. By coexisting, it has been found that the desired isomer product can be obtained without causing metal precipitation with high conversion and high selectivity, and the present invention has been completed.
[0008]
That is, the gist of the present invention is to isomerize an allyl raw material compound having an acyloxy group and / or a hydroxyl group at the allylic position to produce a corresponding allyl isomer product, Platinum compound or palladium compound, and organophosphorus compound Containing catalyst , And In the presence of carboxylic acid In this case, a phosphite compound is used as the organic phosphorus compound, and the abundance ratio (weight ratio) between the carboxylic acid and the total amount of the allyl raw material compound is in the range of 2: 1 to 1:20. The present invention resides in a method for producing an allyl compound, characterized by carrying out an isomerization reaction.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The raw material used in the isomerization reaction of the present invention may be any compound as long as it is an allyl compound having an acyloxy group and / or a hydroxyl group at the allylic position. In the present invention, this raw material causes allylic rearrangement. The corresponding isomer allyl product. Here, the acyloxy group means a general formula R _A C (O) O— and R _A As an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and in particular, R _A Is preferably a methyl group. Specifically, in the present invention, an allylic raw material compound selected from the following formulas (a), (b) and mixtures thereof is subjected to isomerization reaction, and the corresponding formulas (b) and ( Allyl isomer products selected from a) and mixtures thereof can be prepared.
[0010]
[Chemical 2]

[0011]
In the above formulas (a) and (b), R is an acetoxyl group or a hydroxyl group, and R ¹ ~ R ^Five Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, or a carbon number. An aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl aryl group having 6 to 20 carbon atoms, an alkyl aryloxy group having 6 to 20 carbon atoms, an arylalkoxy group having 6 to 20 carbon atoms, a cyano group, An ester group having 2 to 20 carbon atoms, a hydroxy group, or a halogen atom, which may have a substituent. R ¹ ~ R ^Five Examples of the substituent that may have include an alkoxy group having 1 to 10 carbon atoms, a carboxyl group, a hydroxyl group, and an aryl group having 6 to 10 carbon atoms.
[0012]
In the above formula (a), the formula (a ′): CH ₂ = CH-CHR ⁶ -CH ₂ R ⁷ 3,4-disubstituted butene-1 (where R is ⁶ And R ⁷ Is an acetoxyl group or a hydroxyl group. And in the above-mentioned formula (b), the formula (b ′): CH ₂ R ⁸ -CH = CH-CH ₂ R ⁹ 1,4-disubstituted butene-2 (where R is ⁸ And R ⁹ Is an acetoxyl group or a hydroxyl group. ) Is preferred.
Specific examples of 3,4-disubstituted butene-1 of the formula (a ′) include 3,4-diacetoxybutene-1, 3-butene-1,2-diol monoacetoxylate, 3,4-dihydroxy Butene-1, and 1,4-disubstituted butene-2 of the formula (b ′) includes 1,4-diacetoxybutene-2, 1-acetoxy-4-hydroxy-2-butene, 1 , 4-dihydroxybutene-2.
[0013]
In addition, 3,4-diacetoxybutene-1 which is an example of the raw material is obtained by a known method, for example, by reacting butadiene with acetic acid and oxygen in the presence of a catalyst such as palladium, to produce 1,4-diacetoxybutene-2. Can be produced according to, for example, (Japanese Patent Publication No. 51-23008 or 59-28553).
The raw material may be a pure product, but may be a mixture of a plurality of allyl compounds, and includes other components that do not interfere with the isomerization reaction described later, such as acetic acid and water, in addition to the raw material allyl compound. It may be a mixture.
[0014]
The isomerization catalyst used in the reaction of the present invention contains a metal compound of Groups 8 to 10 (IUPAC Inorganic Chemical Nomenclature Revised Edition (1989)) of the periodic table. Examples of the metal compound include one or more compounds selected from compounds of iron, cobalt, nickel, ruthenium, rhodium, platinum, iridium, osmium, and palladium. Among these, nickel, palladium, and platinum compounds are included. More preferred is a palladium compound.
Examples of the metal compound include acetate, acetylacetonate, halide, sulfate, nitrate, organic salt, inorganic salt, alkene compound, amine compound, pyridine compound, phosphine coordination compound, phosphite coordination compound, and the like. .
[0015]
Ruthenium compounds include RuCl _Three , Ru (OAc) _Three , Ru (acac) _Three , RuCl ₂ (PPh _Three ) _Three As the osmium compound, OsCl _Three , Os (OAc) _Three Examples of rhodium compounds include RhCl _Three , Rh (OAc) _Three , Rhodium diacetate dimer, Rh (acac) (CO) ₂ , [Rh (OAc) (COD)] ₂ , [RhCl (COD)] ₂ , Rh (COD) OAc and the like.
Further, as the iridium compound, IrCl _Three , Ir (OAc) _Three As the nickel compound, NiCl ₂ , NiBr ₂ , Ni (NO _Three ) ₂ , NiSO _Four , Ni (COD) ₂ NiCl ₂ (PPh _Three ) ₂ Etc.
[0016]
Examples of the palladium compound include Pd (0) and PdCl. ₂ , PdBr ₂ , PdCl ₂ (COD), PdCl ₂ (PPh _Three ) ₂ , Pd (PPh _Three ) _Four , Pd ₂ (Dba) _Three ・ CHCl _Three , K ₂ PdCl _Four , K ₂ PdCl ₆ (Potassium hexachloropalladate (IV)), PdCl ₂ (PhCN) ₂ , PdCl ₂ (CH _Three CN) ₂ , Pd (dba) ₂ , Pd2 (dba) _Three , Pd (NO _Three ) ₂ , Pd (OAc) ₂ , Pd (CF _Three COO) ₂ , PdSO _Four , Pd (acac) ₂ , Carboxylate compounds, olefin-containing compounds, Pd (PPh _Three ) _Four Organic phosphine-containing compounds, such as allyl palladium chloride dimer, and the like. Among these, Pd (OAc) ₂ , PdCl ₂ Palladium carboxylate compounds or halides are preferred.
Platinum compounds include Pt (acac) ₂ , PtCl ₂ (COD), PtCl ₂ (CH _Three CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt (PPh _Three ) _Four , K ₂ PtCl _Four , Na ₂ PtCl ₆ , H ₂ PtCl ₆ Etc. (Here, COD: cyclopentadiene, dba: dibenzylideneacetone, acac: acetylacetonate)
In the present invention, the form of the metal compound described above is not particularly limited, and the active metal complex species may be a monomer, a dimer and / or a multimer.
[0017]
Although there is no restriction | limiting in particular about the usage-amount of these metal compounds, From a catalyst activity and economical viewpoint, it is 1x10 with respect to the allyl compound which is a reaction raw material. ^-8 (0.01 mole ppm) to 1 mole equivalent, preferably 1 × 10 ^-7 (0.1 mol ppm) to 0.001 molar equivalent range, particularly preferably 10 ^-6 Used in a range of up to 0.0001 molar equivalents.
[0018]
In the present invention, a carboxylic acid such as a fatty acid having 2 to 8 carbon atoms or an aromatic carboxylic acid having 6 to 12 carbon atoms is present in the isomerization reaction system using the catalyst containing the specific metal compound described above. , Has the advantage of promoting the isomerization reaction. Of these, fatty acids having 2 to 6 carbon atoms such as acetic acid, propionic acid and butyric acid are preferable, and acetic acid is most preferable. The abundance of the carboxylic acid is generally 10: 1 to 1: 1000 in terms of the total amount (weight ratio) of allyl raw material compound which is acetic acid: raw material from the viewpoint of catalyst activity, catalyst stability and economy, preferably Is in the range of 4: 1 to 1: 100, more preferably 2: 1 to 1:20.
In the present invention, a carboxylic acid must be separately present even when the aryl raw material compound for isomerization has a carboxyl group as a substituent.
[0019]
In the present invention, it is preferable to use an organophosphorus compound as a catalyst component together with the metal compound described above. Examples of the organophosphorus compound include monodentate or polydentate phosphines, phosphites, phosphonites, phosphinites, etc. Among them, phosphite compounds are preferable. The phosphite compound is not particularly limited, but preferred phosphite compounds include those represented by the following general formulas (I), (II), (III), (IV), (V) and (VI). Is at least one kind.
[0020]
[Chemical 3]

[0021]
In the formulas (I) to (VI), R ^Ten ~ R ^{twenty one} Each independently represents an alkyl group, an alkoxy group, a cycloalkyl group, an aryloxy group, an alkylaryloxy group, an arylalkoxy group, or an aryl group, and may further have a substituent.
[0022]
R ^Ten ~ R ^{twenty one} When an alkyl group is used, or when a substituent having an alkyl skeleton (such as an alkyl group in an alkyl aryloxy group) is used, the carbon number is usually 1-20, preferably 1-14. . Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, hexyl group, octyl group, decyl group. Group. In addition, the alkyl group or the alkyl skeleton may further have a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an amino group, a cyano group, and carbon. Examples of the ester group, hydroxy group, and halogen atom of 2 to 10 are mentioned.
[0023]
R ^Ten ~ R ^{twenty one} When an aryl group is used as a substituent or a substituent having an aryl skeleton is used, the number of carbon atoms is usually 6 to 20, preferably 6 to 14. Specific examples include a phenyl group, a tolyl group, a xylyl group, a di-t-butylphenyl group, a naphthyl group, and a di-t-butylnaphthyl group.
The aryl group or the aryl skeleton may further have a substituent, and examples of the substituent include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkyl group having 3 to 20 carbon atoms. A cycloalkyl group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 6 to 20 carbon atoms, an alkylaryloxy group having 6 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms Examples thereof include an alkyl group, an arylalkoxy group having 6 to 20 carbon atoms, a cyano group, an ester group having 2 to 20 carbon atoms, a hydroxy group, and a halogen atom.
[0024]
R ^Ten ~ R ^{twenty one} Specific examples of these include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group. 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 4-trifluoromethylphenyl group, 2 -Methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl Groups and the following (C-1) to (C-8).
[0025]
[Formula 4]

[0026]
Z ¹ ~ Z ^Four And A ¹ ~ A ^Three Are each independently an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, or -Ar. ¹ -(Q ¹ ) _n -Ar ² A diarylene group (provided that Ar may have a divalent linking group in the middle) ¹ And Ar ² Each independently represents an arylene group having 6 to 18 carbon atoms which may have a substituent. ). T is a carbon atom, an alkanetetrayl group, a benzenetetrayl group, or T ² -(Q ² ) _n -T ² A tetravalent group which may have a substituent represented by T ¹ And T ² Each independently represents a trivalent organic group which may have a substituent selected from an alkanetriyl group having 1 to 10 carbon atoms and a benzenetriyl group having 6 to 15 carbon atoms. Q ¹ And Q ² Are each independently -CR ^{twenty two} R ^{twenty three} -, -O-, -S- or -CO-, n is 0 or 1, R ^{twenty two} And R ^{twenty three} Are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and may have a substituent.
[0027]
Z ¹ ~ Z ^Four Or A ¹ ~ A ^Three When is an alkylene group, specific examples thereof include, for example, a tetramethylethylene group and a dimethylpropylene group. When Z is an alkylene group which may have a substituent, the substituent has 1 carbon atom. -10 alkoxy group, aryl group having 6 to 10 carbon atoms, amino group, cyano group, amide group, nitro group, trifluoromethyl group, trimethylsilyl group, ester group having 3 to 10 carbon atoms, hydroxy group and halogen atom. Can be mentioned.
Z ¹ ~ Z ^Four Or A ¹ ~ A ^Three In the case of an arylene group which may have a substituent, specific examples thereof include a phenylene group and a naphthylene group, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms and a carbon number. 1-10 alkoxy groups, C6-C10 aryl groups, amino groups, cyano groups, C2-C10 ester groups, amide groups, nitro groups, trifluoromethyl groups, trimethylsilyl groups, hydroxy groups, and halogen atoms Etc.
Furthermore, Z ¹ ~ Z ^Four Or A ¹ ~ A ^Three -Ar ¹ -(Q) _n -Ar ² In the case of a diarylene group which may have a divalent linking group in the middle of ¹ And Ar ² Is an arylene group which may have a substituent, and the carbon number thereof is preferably 6 to 24, more preferably 6 to 16, and specific examples of the substituent include a C 1 to C 10 alkyl group and a carbon number of 1 -10 alkoxy groups, C6-C10 aryl groups, amino groups, cyano groups, C2-C10 ester groups, hydroxy groups, halogen atoms, and the like.
A ¹ ~ A ^Three And Z ¹ ~ Z ^Four As a specific example,-(CH ₂ ) ₂ -,-(CH ₂ ) _Three -,-(CH ₂ ) _Four -,-(CH ₂ ) _Five -,-(CH ₂ ) ₆ -, -CH (CH _Three ) -CH (CH _Three )-, -CH (CH _Three ) CH ₂ CH (CH _Three )-, -C (CH _Three ) ₂ -C (CH _Three ) ₂ -, -C (CH _Three ) ₂ -CH ₂ -C (CH _Three ) ₂ -And following (A-1)-(A-46) are mentioned. Moreover, (A-47) is also mentioned as a specific example of A1 to A3.
[0028]
[Chemical formula 5]

[0029]
[Chemical 6]

[0030]
[Chemical 7]

[0031]
[Chemical 8]

[0032]
[Chemical 9]

[0033]
[Chemical Formula 10]

[0034]
And the following (1)-(12) and (P1)-(P21) can be illustrated as a preferable specific example of the compound of Formula (I)-(VI).
[0035]
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[0036]
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[0037]
Embedded image

[0038]
Embedded image

[0039]
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[0040]
Embedded image

[0041]
Specific examples of phosphines include triphenylphosphine, tri (normal butyl) phosphine, tri (t-butyl) phosphine, diphenylphosphinoethane, diphenylphosphinomethane, diphenylphosphinopropane, diphenylphosphinobutane and the following ( 13) to (20) can be exemplified.
[0042]
Embedded image

[0043]
Moreover, as phosphonites and phosphinites, the following (21) to (35) can be exemplified.
[0044]
Embedded image

[0045]
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[0046]
Embedded image

[0047]
The ratio (molar ratio) of these organophosphorus compounds to the metal compound in the isomerization reaction system is usually 0.1 to 10,000, preferably 0.5 to 500, particularly preferably 1.0 to 100. Used in range. The metal compound and the organic phosphorus compound may be added to the reaction system alone or may be used in a complexed state in advance.
[0048]
The isomerization reaction is usually carried out in a liquid phase and can be carried out in the presence or absence of a solvent, but it is usually preferred to carry out the isomerization reaction in a homogeneous system using a solvent. The solvent is not particularly limited as long as it can dissolve the catalyst and the raw material compound.
[0049]
Specific examples of the solvent include, for example, carboxylic acids such as acetic acid, alcohols such as methanol, diglyme, diphenyl ether, dibenzyl ether, tetrahydrofuran (THF), ethers such as dioxane, N-methylpyrrolidone (NMP), dimethylformamide. (DMF), amides such as dimethylacetamide, ketones such as cyclohexanone, esters such as butyl acetate, γ-butyrolactone, di (n-octyl) phthalate, aromatic hydrocarbons such as toluene, xylene, dodecylbenzene, Examples thereof include high-boiling products produced as by-products in the isomerization reaction system, and allyl compounds themselves as raw materials. Among these, it is preferable to use a carboxylic acid such as acetic acid as defined in the present invention as a solvent in terms of promoting the isomerization reaction.
Although the usage-amount of these solvents is not specifically limited, Usually, it is 0.1-20 weight times with respect to the total amount of the allyl compound which is a raw material, Preferably it is 0.5-10 weight times.
[0050]
In the present invention, the reaction for obtaining 1,4-diacetoxybutene-2 by isomerization of 3,4-diacetoxybutene-1 is an equilibrium reaction, and the equilibrium mixture at 120 ° C. is about 60 to 65 mol%. 1,4-diacetoxybutene-2 and 35-40 mol% 3,4-diacetoxybutene-1. This means that a reaction mixture containing 1,4-diacetoxybutene-2 as the main component is subjected to an isomerization reaction to obtain a product containing 3,4-diacetoxybutene-1 as the main component. It means that.
[0051]
The range of the molar ratio of 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 in the product obtained by the isomerization reaction is usually from 90:10 to 10:90. The product of any ratio such as 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, and 20:80 can be produced. This ratio is not particularly limited, but can be adjusted depending on reaction conditions and process economics.
[0052]
The isomerization reaction system of the present invention may contain reaction by-products other than raw materials and substrates, decomposition products of catalysts, and the like.
Specifically, in the isomerization reaction system, butanediol monoacetoxylate, 1-acetoxybutan-2-one, 4-acetoxybutanal, 4-acetoxycyclotonaldehyde, diacetoxybutane, acetoxyhydroxybutane, butanediol, One or more compounds (C) selected from 1,4-butenediol, 1,2-butenediol, 1-acetoxy-1,3-butadiene, and diacetoxyoctadiene may be present.
In the isomerization reaction system, these compounds (C) are usually (1: 1 to 1: 10000) in a weight ratio (compound (C): allyl compound) to the total amount of allyl compounds as raw materials, preferably May be in the range of 5: 1 to 1: 1000, more preferably 2: 1 to 1: 500, particularly preferably 0.1: 1 to 1: 100.
[0053]
In the present invention, if a large amount of water is present in the isomerization reaction system, the isomerization reaction is remarkably inhibited. Therefore, a smaller amount of water is preferable in that the conversion rate is increased. In order to completely exclude water from water, extremely large energy is required. Therefore, industrially, the abundance of water in the isomerization reaction mixture is preferably 0.1 to 5 wt%, more preferably 0.5 to 2 wt%. Water can be mixed into the reaction system from various routes, but among them carboxylic acids used as solvents or accelerators for isomerization reactions are often accompanied by water. In such a case, the weight ratio of water to carboxylic acid is preferably 1 or less.
[0054]
The present invention provides a reaction product comprising 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene obtained by diacetoxylation of butadiene in the presence of acetic acid and oxygen as described above. From 1,4-diacetoxy-1-butene is separated and then isomerized by the method of the present invention to obtain 1,4-diacetoxy-2-butene. Also effective.
[0055]
When a reaction product obtained by such a butadiene diacetoxylation reaction is used as a raw material, 1,4-diacetoxy-2-butene, 3,4-diacetoxy-1-butene and the like are included in the reaction product. In addition to the diacetoxy compound, there is a compound similar to the compound (C) described above. Therefore, the 3,4-disubstituted-1-butene compound or 1,4-disubstituted-2- It is preferable to separate a mixture mainly containing any one component of the butene body, and then to isomerize the mixture.
[0056]
In the mixture containing 3,4-disubstituted-1-butene and / or 1,4-disubstituted-2-butene thus separated by an operation such as distillation, diacetoxy and monoacetoxy However, the monoacetoxy compound has a much lower isomerization reaction rate than the diacetoxy compound. Therefore, when performing an isomerization reaction of such a mixture of a diacetoxy compound and a monoacetoxy compound, 1) perform an acetoxylation reaction (esterification reaction) of the monoacetoxy compound in advance before performing the isomerization reaction; It is preferable to employ a method of performing an isomerization reaction of the mixture containing the obtained diacetoxy compound, or 2) a method of simultaneously performing an acetoxylation reaction (esterification reaction) of a monoacetoxy compound in an isomerization reaction system.
[0057]
The acetoxylation reaction (esterification reaction) of the above-mentioned monoacetoxy compound, such as 3-butene-1,2-diol monoacetoxylate and / or 1-acetoxy-4-hydroxy-2-butene, causes acetic anhydride to be present. It progresses by. The amount of acetic anhydride is not particularly limited, but may be around equimolar with respect to the monoacetoxy compound. When acetic anhydride is used, the reaction temperature of the esterification reaction is usually 40 to 200 ° C, preferably 100 to 160 ° C.
[0058]
The acetoxylation reaction of the monoacetoxy compound described above also proceeds by the presence of an ion exchange resin and acetic acid. By using an ion exchange resin, there is an advantage that an acetoxylation reaction can be carried out without using expensive acetic anhydride. The amount of acetic acid is not particularly limited, but since the reaction is an equilibrium reaction, the conversion rate of the acetoxylation reaction increases as the amount of acetic acid increases.
Examples of the ion exchange resin that can be used include cation exchange resins such as styrene, methacrylic acid, and acrylic acid. Among them, styrene cation exchange resins are preferable. The amount of ion exchange resin used is not particularly limited, but is preferably 0.01 to 5 kg, more preferably 1 kg relative to 1 kg of allyl raw material compound in the case of a batch method, from the viewpoint of catalytic activity and economy. 0.05 to 1 kg, and in the case of a continuous process, the space volume is 1 liter of allyl compound per hour, preferably 0.05 to 10 liters, more preferably 0.2 to 2 liters. It is. When using an ion exchange resin, as esterification reaction temperature, it is 20-200 degreeC normally, Preferably it is 30-120 degreeC, More preferably, it is 40-100 degreeC.
[0059]
When the method 2) in which the acetoxylation reaction (esterification reaction) of the monoacetoxy compound is simultaneously performed in the isomerization reaction system as described above is employed, by using the above acetic anhydride, ion exchange resin and acetic acid, It is possible to carry out the isomerization reaction and the esterification reaction under the same reaction conditions, that is, the isomerization reaction conditions described above.
[0060]
The isomerization method of the present invention can be carried out either batchwise or continuously.
More specifically, the case where the isomerization reaction is carried out batchwise will be described. A catalyst component is dissolved in a solvent, and a raw material mainly composed of, for example, 3,4-diacetoxybutene-1, is introduced into the solvent. Contact with catalyst for sufficient conversion time. After completion of the reaction, the component mainly composed of the desired 1,4-diacetoxybutene-2 and the like can be separated and recovered from the reaction solution by means such as distillation.
Separation of 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 can be usually performed by a method such as distillation or extraction.
[0061]
In the case of carrying out continuously, for example, a raw material mainly composed of 3,4-diacetoxybutene-1 and a catalyst component are continuously supplied to a reaction tank, and a reaction liquid containing an isomerized product as a target product is continuously supplied. It is possible to use a system in which the residual liquid containing the catalyst component is continuously circulated and reused in the reaction system after it is extracted into the water and distilled.
The reaction temperature for isomerization is usually 50 to 200 ° C, preferably 80 to 160 ° C. If the reaction temperature is too low, the activity is low, and if it is too high, the stability of the catalyst is lowered and undesirable side reactions occur. The reaction pressure is not particularly limited and is appropriately selected from the range of normal pressure to 3 MPa, preferably from normal pressure to 2 MPa. The reaction time is not particularly limited, and is appropriately selected in consideration of the reaction rate based on factors such as the amount of catalyst and reaction temperature.
[0062]
The reaction for obtaining the corresponding 1,4-di-substituted product by isomerization of the 3,4-di-substituted product is an equilibrium reaction, and the catalyst serves to bring the reaction raw material composition closer to the equilibrium composition. That is, the effect is the same regardless of whether the starting material is a mixture mainly composed of 3,4-di-substituted or 1,4-di-substituted. Therefore, for the isomerization reaction of components mainly composed of 1,4-diacetoxybutene-2, except that 1,4-diacetoxybutene-2 or a mixture containing the same is used as a raw material, the above-mentioned 3,4- It can be carried out according to an isomerization reaction of a raw material mainly composed of diacetoxybutene-1.
[0063]
According to the present invention, 3,4-disubstituted butene-1 and / or 1,4-disubstituted butene-2 is isomerized in the presence of a catalyst comprising a metal compound of an element of Groups 8-10 of the periodic table. It is possible to obtain the isomerized product in a yield of 10 mol% or more while suppressing the precipitation of the metal compound during the conversion.
[0064]
【Example】
The present invention will be described in more detail below, but the present invention is not limited to the following examples unless it exceeds the gist. The reaction results in the following examples were calculated from the results of analyzing the reaction solution composition by gas chromatography.
When 3,4-diacetoxybutene-1 (hereinafter sometimes abbreviated as 3,4-DABE) is used as a raw material, 1,4-diacetoxybutene-2 (hereinafter, 1,4-DABE) is used as a product. The reaction results were defined as the yield of 1,4-diacetoxybutene-2. Further, as the phosphite compound, the above (P1) to (P21) were used, and all reactions using phosphite were carried out in a nitrogen atmosphere.
[0065]
Examples 1-8
In a 10 ml flask purged with nitrogen, 3,4-diacetoxybutene-1 (3,4-DABE: 0.633 mmol), Pd (OAc) ₂ (0.0221 mmol), the phosphite compound (0.041 mmol) and acetic acid (1 ml: the weight ratio of raw material 3,4-DABE was 9.64, and the mixture was reacted at 80 ° C. for 1 hour. The yield of acetoxybutene-2 (1,4-DABE) is shown in Table 1. In any system, no precipitation of Pd metal was observed.
[0066]
[Table 1]

[0067]
Comparative Example 1
When 1 ml of diglyme was used in place of acetic acid used in Example 3 and the reaction temperature was changed to 120 ° C., the same reaction as in Example 3 was performed. The yield of 1,4-DABE was 56.5%. Met. Also in this case, the deposition of palladium metal could not be observed. Comparing Example 3 and Comparative Example 1, it can be seen that the presence of acetic acid improves the yield of 1,4-DABE.
[0068]
Example 9
Pd (OAc) ₂ (0.633 mmol), (P3) (0.041 mmol) as a phosphite compound, acetic acid (0.037 ml; weight ratio to raw material DABE is 3.56), 1 ml of diglyme and 3,4-diacetoxybutene-1 (3 , 4-DABE) or 1,4-diacetoxybutene-2 (1,4-DABE) was charged in an amount of 0.633 mmol, and the reaction was carried out at 68 ° C. It was found that the isomerization reaction was completed in about 100 minutes for both raw materials and the equilibrium concentration was reached. Again, no palladium deposition was observed as long as the phosphite compound was present.
[0069]
Examples 10-12 (Pd system, P19-21 usage example)
In 1 ml (6.3 mmol) of 3,4-diacetoxybutene-1 Pd (OAc) ₂ 21 μmol (5 mg) and 12 mg each of the phosphite compounds (P19) to (P21) were dissolved, and then acetic acid (10 μl; the weight ratio to the raw material DABE was 0.0968) was added and reacted at 120 ° C. for 30 minutes. The results are shown in Table 2 below. In any system, no precipitation of Pd metal was observed.
[0070]
[Table 2]

[0071]
Example 13 (Pd system, using P13)
3.7 mg (6.4 μmol) of Pd (dba) 2 and 40 mg (51 μmol) of the phosphite compound (P13) were dissolved in 11,4-diacetoxybutene-11 ml (6.3 mmol) at 120 ° C. 10 μl of the solution was added to another Schlenk tube containing acetic acid (1 ml; weight ratio to raw DABE: 9.59) and 3,4-diacetoxybutene-1 1 ml (6.3 mmol) and reacted at 120 ° C. for 3 hours I let you. The molar balance was 99% or more, and when the reaction product solution was analyzed, 62% of 1,4-DABE and 38% of 3,4-DABE were contained. In this reaction, no precipitation of Pd metal was observed.
[0072]
Example 14 (Influence of the amount of acetic acid)
The concentrations of Pd (OAc) shown in Table 3 below ₂ And 4 molar equivalents of bisphosphite (P4) with respect to Pd was added to a flask containing acetic acid in the amount shown in Table 3 and 1 ml (6.3 mmol) of 3,4-DABE, and reacted at 120 ° C. for 1 hour. It was. The results are shown in Table 3. In this reaction, no precipitation of Pd metal was observed.
[0073]
[Table 3]

*: The reaction time was 15 minutes.
^** : The value in [] represents the weight ratio of acetic acid to the raw material DABE.
From the results of Table 3, it can be seen that the molar balance is as high as 98% or more in the region where the concentration of acetic acid is high, that is, the region where the concentration of Pd compound is low.
[0074]
Example 15 (Pt system, using phosphite P13)
In 1 ml (6.3 mmol) of 3,4-diacetoxybutene-1 Pt (acac) ₂ 2.5 mg (6.21 μmol) and 10 mg (13 μmol) of the phosphite compound (P13) were dissolved, and then acetic acid (1 ml; the weight ratio to the raw material DABE was 9.68) was added and reacted at 120 ° C. for 1 hour. It was. As a result of GC analysis of the reaction product solution, 17 mol% (tranc / cis = 4.5) of 1,4-DABE and 83 mol% of 3,4-DABE were contained. In this reaction, no precipitation of Pt metal was observed.
[0075]
Example 16 (Rh system, using phosphite P13)
[Rh (COD) OAc] in 1 ml (6.3 mmol) of 3,4-diacetoxybutene-1 ₂ 1.8 mg (3.5 μmol) and 10 mg (13 μmol) of the phosphite compound (P13) were dissolved, and then acetic acid (1 ml; the weight ratio to the raw material DABE was 9.68) was added and reacted at 120 ° C. for 1 hour. . As a result of GC analysis of the reaction product solution, it was found that 6,4-DABE was 6.3% (tranc / cis = 4.3) and 3,4-DABE was 92%. In this reaction, no precipitation of Rh metal was observed.
[0076]
Comparative Example 2
To a 10 ml flask purged with nitrogen, 3,4-diacetoxybutene-1 (0.633 mmol), Pd (OAc) ₂ (0.06 mmol) and 1 ml of diglyme were used for reaction for 1 hour at a reaction temperature of 120 ° C., and the yield of 1,4-DABE was 1.3%. However, a palladium metal mirror was observed on the flask surface after completion of the reaction.
[0077]
【The invention's effect】
According to the present invention, an allyl raw material compound such as 3,4-disubstituted butene-1 and / or 1,4-disubstituted butene-2 is added in the presence of a catalyst containing a group 8-10 metal compound and a carboxylic acid. 1,4-disubstituted butene-2 and / or 3,4-disubstituted, which is a corresponding isomer, with high conversion, high selectivity, and suppression of metal precipitation. Butene-1 etc. can be manufactured.
[Brief description of the drawings]
1 is a graph showing the isomerization reaction rates of 3,4-diacetoxybutene-1 and 1,4-diacetoxybutene-2 in Example 9. FIG.

Claims (12)

A method for producing allyl isomer product corresponding to isomerization of allyl starting material compound having the acyloxy group and / or hydroxyl group in allyl position, the presence of a catalyst, and a carboxylic acid containing a platinum compound or a palladium compound, and an organic phosphorus compound The isomerization reaction is performed by using a phosphite compound as the organic phosphorus compound and setting the abundance ratio (weight ratio) between the carboxylic acid and the total amount of the allyl raw material compound in the range of 2: 1 to 1:20. A method for producing an allyl compound. The method for producing an allyl compound according to claim 1, wherein the carboxylic acid is a fatty acid having 2 to 8 carbon atoms. The allyl raw material compound is 3,4-disubstituted butene-1, represented by the formula (a ′): CH ₂ ═CH—CHR ⁶ —CH ₂ R ⁷ , formula (b ′): CH ₂ R ⁸ —CH═ method for producing a CH-CH ₂ R -2 and represented by 1,4-disubstituted butene ⁹ allyl compounds according to claim 1 or 2 in which selected mixtures thereof. (However, in the formulas (a ′) and (b ′), R ^{6 to} R ⁹ are groups selected from an acetoxyl group and a hydroxyl group, and may be the same or different.) The allyl isomer product is a 1,4-disubstituted butene-2 represented by the formula (b ′): CH ₂ R ⁸ —CH═CH—CH ₂ R ⁹ , the formula (a ′): CH ₂ ═CH -CHR ⁶ -CH ₂ method for producing allyl compound according to any one of claims 1 to 3 represented by R ⁷ is 3,4-disubstituted butene-1 and those selected from mixtures thereof. (However, in the formulas (a ′) and (b ′), R ^{6 to} R ⁹ are groups selected from an acetoxyl group and a hydroxyl group, and may be the same or different.) The method for producing an allyl compound according to any one of claims 1 to 4 , wherein the allyl raw material compound of the formula (a ') is isomerized into an allyl isomer product of the formula (b'). The method for producing an allyl compound according to any one of claims 1 to 4 , wherein the allyl raw material compound of the formula (b ') is isomerized into an allyl isomer product of the formula (a'). A mixture based on 3,4-diacetoxybutene-1 and 3-butene-1,2-diol monocarboxylate is isomerized to give 1,4-diacetoxybutene-2 and 1-acetoxy-4-hydroxy- The method for producing an allyl compound according to any one of claims 1 to 5 , wherein a reaction product containing 2-butene is obtained. Method for producing a phosphite compound, an allyl compound according to claim 1 is at least one selected from the group consisting of the following general formula (I) ~ (VI) with the indicated Ru of compounds.

(In the formulas (I) to (VI), R ^{10 to} R ²¹ each independently represents an alkyl group, an alkoxy group, a cycloalkyl group, an aryloxy group, an alkyl aryloxy group, an arylalkoxy group, or an aryl group. Furthermore, Z ^{1 to} Z ⁴ and A ^{1 to} A ³ each independently have an alkylene group and a substituent which may have a substituent. Or an arylene group which may have a divalent linking group in the middle of —Ar ¹ — (Q ¹ ) _n —Ar ² — (Ar ¹ and Ar ² are each independently Represents an arylene group having 6 to 18 carbon atoms which may have a substituent, and T represents a carbon atom, an alkanetetrayl group, a benzenetetrayl group, or T ¹ — (Q ² ) _n —. A tetravalent group optionally having a substituent represented by T ² Each of T ¹ and T ² independently represents a trivalent organic group which may have a substituent selected from an alkanetriyl group and a benzenetriyl group, Q ¹ and Q ² are Each independently represents —CR ²² R ²³ —, —O—, —S— or —CO—, n is 0 or 1, R ²² and R ²³ each independently represents a hydrogen atom, an alkyl; Group or aryl group, which may have a substituent.) The method for producing an allyl compound according to claim 8 , wherein the phosphite compound is a compound represented by the general formula (IV). The method for producing an allyl compound according to claim 8 , wherein the phosphite compound is a compound represented by the general formula (V). The method for producing an allyl compound according to claim 8 , wherein the phosphite compound is a compound represented by the general formula (VI). In any one of the general formulas (IV) to (VI), R ^{16 to} R ²¹ each represents an optionally substituted aryl group having 6 to 20 carbon atoms, and Z ^{1 to} Z ⁴ are each independently A diarylene group which may have a divalent linking group in the middle of -Ar ^1- (Q ¹ ) _n -Ar ² — (wherein Ar ¹ and Ar ² each independently have a substituent) Represents an arylene group having 6 to 18 carbon atoms, Q ¹ independently represents —CR ²² R ²³ —, —O—, —S— or —CO—, and n is 0 or 1 , R ²² and R ²³ each independently represents a hydrogen atom, an alkyl group or an aryl group, and A ^{1 to} A ³ are bisarylene having 12 to 20 carbon atoms which may have a substituent. method for producing allyl compounds according to any of the claims 9-11 representing the group.

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