505626 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（i) 本發明是有關於一種催化丁二烯酯化反應以生成 3-烯基戊酸酯類化合物之觸媒。 使用丁一婦為原料’並在過渡金屬催化劑的催化下 進行酯化反應以生成烯基戊酸甲酯類化合物為一已知的 技術，但此技術一般會生成3-烯基戊酸酯與2-烯基戊酸 酯之混合物。有鑑於此，本發明提出一種新型之酯化觸 媒配方，可將丁二烯有效地酯化並生成高純度的3_烯基 戊醋類化合物 習知一種選擇性製備烯類_羧酸衍生物之製程揭露 於美國專利US Patent No:5,02《734，其使用鈀金屬、雙 磷配位基以及苯甲酸所構成觸媒配方，用以酯化丁二嫦 ，生成約75%的3-丁二烯戊酸甲酯以及25%的2-烯基 戊酸甲酯。本發明之缺點在於此類觸媒在一氧化碳與烧 基醇類存在的條件下進行酯化反應，往往會將苯甲酸之 羧酸官能基酯化：505626 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (i) The present invention relates to a catalyst that catalyzes the esterification of butadiene to form 3-alkenylvalerate compounds. It is a known technique to use butyrate as a raw material and to perform an esterification reaction under the catalysis of a transition metal catalyst to form methyl alkenyl valerate, but this technology generally generates 3-alkenyl valerate and A mixture of 2-alkenylvalerates. In view of this, the present invention proposes a novel esterification catalyst formulation, which can effectively esterify butadiene and generate high-purity 3-alkenylpentanoate compounds. The manufacturing process of the material is disclosed in US Patent No: 5,02 "734, which uses a catalyst formula composed of palladium metal, double phosphorus ligands and benzoic acid to esterify succinic acid to generate about 75% of 3 -Methyl butadiene valerate and 25% methyl 2-alkenyl valerate. The disadvantage of the present invention is that such catalysts undergo esterification in the presence of carbon monoxide and alcohols, often esterifying the carboxylic acid functional groups of benzoic acid:
COOHCOOH
、OR 因此，此類觸媒之苯甲酸易被酯化生成苯曱酸酯類 化合物，故必須經常重複補充苯甲酸以維持觸媒的高活 性。此外，利用此觸媒也會生成一種不易進行醛化反應 之產物：2-烯基戊酸酯。 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、τ 505626 A7 B7 五、發明説明（2) 習知另一種製備3 -烯基戊酸甲酯的製程揭露於 美國專利US Patent ΝΟ·5,495,041，其主要是利用#巴 金屬、雙磷配位基與 3-烯基戊酸之觸媒配方，用以 酯化丁二烯，其中丁二烯之轉化率較低，約80% ; 而 3-烯基戊酸甲酯之選擇性則小於50%。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 本發明之特徵在於利用含巨大立體效應之官能 基的苯甲酸為共催化劑，例如 2,4,6-三異丙基苯甲 酸，以進行酯化反應。經過實驗後，證實此類苯甲 酸不會在酯化條件下被醇類或甲酸所酯化，且重複 使用後仍具有高催化活性，不需額外的水解及回收 處理便可再加入丁二烯接著進行酯化反應，且不需 經常添加額外的苯甲酸所構成之共催化劑，具有高 可再利用性。此外，利用本發明所提出之酯化反應 觸媒，其對 3 -烯基戊酸酯之選擇性高，經過酯化反 應後的產物為純度> 9 7 %之3 -烯基戊酸酯。由於2 -烯基戊酸酯不易進行醛化反應（反應活性為3 -烯基戊 酸醛之 1 /6 )，且2 -烯基戊酸醛酯易與氡反應，生成 過氧化物，毒化醛化反應的觸媒，故開發3-烯基戊 酸酯之酯化反應觸媒配方，將可明顯改善生產製程， 並降低生產成本。 本發明之特徵是提出一種催化丁二烯酯化反應 以生成3-烯基戊酸酯類化合物之觸媒組合物，包括： 一種鈀錯合物；一種雙配位基磷配位體，具有通式： _^_4_.___ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 505626 A7 B7 五、發明説明（3 ) HP — (CH2)n — PR3R4，其中η為1〜6其中之一的 整數，Ri、R2、R3、R4為含苯基之取代基或聯苯化 合物；以及一種含高立體效應官能基之苯甲酸。其 中該鈀錯合物是選自醋酸鈀、乙醯丙酮鈀、及六氟 乙醯丙酮鈀化合物所構成之族群，且鈀錯合物之含 量約為0.1至10莫耳份；該雙配位基磷配位體是選 自α，α’-二苯基磷-鄰-二甲苯以及雙（二苯基磷甲 基）-1，1 ’ -二苯基所構成之族群，且其雙配位基磷配 位體之含量約為0.6至60莫耳份；該含高立體效應 官能基之苯甲酸是選自2,4,6-三異丙基苯.甲基羧酸， 2,6-二異丙基苯甲基羧酸，2,6-三-肆-丁基苯甲基羧 酸及2,6-二異丙基苯甲基羧酸所構成之族群，且該 含高立體效應官能基之苯甲酸含量約為 5.0至 100 莫耳份。 本發明的觸媒組合物已描述如上，為使本發明 更淺顯易懂，玆將配合相關的實施例，詳細說明於 後。 經濟部中央標準局員工消費合作社印製 (請先閎讀背面之注意事項再填寫本頁) 較佳實施例： 實施例1 : 一個容量 150ml的壓力鍋經過真空乾燥後，通 入氮氣，此反應器接著並加入 〇.〇6g (0.27mmol)的 醋酸鈀、0.51 g (1.08mmol)的α，α’-二苯基磷-鄰二甲 _^^_5_.__ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） A7 B7 五、發明説明（4 ) 苯〇.47$(1.89111111〇1)的2,4,6-三異丙基苯甲酸、5〇1111 的一苯基甲醇（作為鈍性溶劑）、2 ig (6563mm〇l)的 (請先聞讀背面之注意事項再填寫本頁) 甲醇以及5ml的丁二烯（57.3 mm〇i)。接著，將壓力 鍋加熱到15(TC，然後通入壓力6〇atm之二氧化碳以 起始反應，然後在溫度保持在15〇t以及6〇atm的一 氧化礙環境下進行幾化反應、3 ^'時。分析所得到的 反應溶液後顯示’ 丁二烯的轉化率約為㈣，而對 所要的3-戊烯醋之選擇性約為93%，對2戊烯醋的 選擇性約為3.5%。 實施例2 · 經濟部中央標準局員工消費合作社印製 實施例1之反應溶液以真空蒸餾法去除揮發性 物質，所獲得之反應產物約有94%的3_戊烯酯，3% 的2-戊烯酯以及3%的丁二烯二聚物。為了檢查觸 媒系統的穩定度，2. lg的曱醇以及5nU的丁二烯被 加入反應器内’然後進行重複的幾化反應。反應是 在溫度15(TCU A 6〇atm㈣一氧化碳的i免下進行3 小時’然後將反應器冷卻至室溫。分析反應溶液後 可發現，丁二烯的轉換率為85%，而對所要的3_戊 烤醋之選擇性約| 93%，對2_戊稀醋的選擇性約為 3.5%。纟重複的反應結果中顯示，此類觸媒的催化 活性以及選擇性均保持一致。Therefore, the benzoic acid of such catalysts is easily esterified to form benzoate compounds. Therefore, benzoic acid must be replenished frequently to maintain the high activity of the catalyst. In addition, the use of this catalyst will also produce a product that is difficult to carry out the aldehyde reaction: 2-alkenylvalerate. This paper size applies to Chinese national standards (CNS> A4 size (210X297 mm) (Please read the precautions on the back before filling out this page), τ 505626 A7 B7 V. Description of the invention (2) Learn another way to prepare 3 -ene The process of methyl valproate is disclosed in US Patent No. 5,495,041, which is mainly a catalyst formulation using #bar metal, bisphosphonium ligand and 3-alkenylvaleric acid to esterify butadiene, Among them, the conversion rate of butadiene is low, about 80%; and the selectivity of methyl 3-alkenylvalerate is less than 50%. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page) The present invention is characterized by using a benzoic acid containing a functional group with a large stereo effect as a co-catalyst, such as 2,4,6-triisopropylbenzoic acid, to perform an esterification reaction. After experiments, this is confirmed Benzoic acid is not esterified by alcohols or formic acid under esterification conditions, and still has high catalytic activity after repeated use. Without additional hydrolysis and recovery treatment, butadiene can be added and then esterified. No need to add extra benzyl often The co-catalyst composed of acid has high reusability. In addition, the esterification reaction catalyst proposed by the present invention has high selectivity to 3-alkenylvalerate, and the product after the esterification reaction is Purity> 97% of 3-alkenylvalerate. Since 2-alkenylvalerate is not easy to undergo aldolization reaction (reactivity is 1/6 of 3-alkenylvaleraldehyde aldehyde), and 2-alkenyl Valproic acid aldehyde esters easily react with osmium to form peroxides and poison the catalysts of the aldolization reaction. Therefore, the development of a 3-alkenylvalerate esterification catalyst formulation can significantly improve the production process and reduce the production cost. A feature of the present invention is to provide a catalyst composition that catalyzes the butadiene esterification reaction to form a 3-alkenylvalerate compound, comprising: a palladium complex; a double-ligand phosphorus ligand, It has the general formula: _ ^ _ 4 _.___ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 505626 A7 B7 V. Description of the invention (3) HP — (CH2) n — PR3R4, where η is 1 ~ An integer of one of 6, Ri, R2, R3, and R4 are phenyl-containing substituents or biphenyl compounds; A benzoic acid containing a high stereo effect functional group, wherein the palladium complex is selected from the group consisting of palladium acetate, acetone acetone palladium, and hexafluoroacetone acetone palladium compound, and the content of the palladium complex is approximately 0.1 to 10 moles; the di-ligand phosphorus ligand is selected from the group consisting of α, α'-diphenylphospho-o-xylene and bis (diphenylphosphomethyl) -1,1'-di A group of phenyl groups, and the content of the bi-ligand phosphorus ligands is about 0.6 to 60 moles; the benzoic acid containing a high stereo effect functional group is selected from 2,4,6-triisopropyl Benzylbenzene. Methylcarboxylic acid, 2,6-diisopropylbenzylcarboxylic acid, 2,6-tri-methyl-butylbenzylcarboxylic acid and 2,6-diisopropylbenzylcarboxylic acid A group of acids, and the content of the benzoic acid containing the high stereo effect functional group is about 5.0 to 100 moles. The catalyst composition of the present invention has been described as above. In order to make the present invention more comprehensible, related embodiments are described in detail below. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Preferred embodiment: Example 1: A 150ml pressure cooker is vacuum-dried, and nitrogen is passed through the reactor. Then, 0.06 g (0.27 mmol) of palladium acetate and 0.51 g (1.08 mmol) of α, α'-diphenylphosphine-o-dimethylformate are added. This paper is in accordance with the Chinese National Standard (CNS ) A4 specification (210X297 mm) A7 B7 V. Description of the invention (4) Benzene 0.47 $ (1.89111111〇1) 2,4,6-triisopropylbenzoic acid, 501011 monophenyl methanol ( As an inert solvent), 2 ig (6563mm〇l) of methanol (please read the precautions on the back before filling in this page) methanol and 5ml of butadiene (57.3mm〇i). Next, the pressure cooker was heated to 15 ° C, and then carbon dioxide at a pressure of 60atm was introduced to initiate the reaction, and then the reaction was carried out under the environment of a temperature of 150t and a temperature of 60atm, which caused a chemical reaction of 3 ^ ' The analysis of the obtained reaction solution showed that the conversion of butadiene was about ㈣, and the selectivity to the desired 3-pentene vinegar was about 93%, and the selectivity to 2-pentene vinegar was about 3.5%. Example 2 · The consumer solution of the Central Standards Bureau of the Ministry of Economic Affairs printed the reaction solution of Example 1 to remove volatile substances by vacuum distillation. The reaction product obtained was about 94% 3-pentenyl ester and 3% 2 -Pentenyl ester and 3% butadiene dimer. In order to check the stability of the catalyst system, 2. lg of methanol and 5 nU of butadiene were added to the reactor 'and then repeated several chemical reactions were performed. The reaction was carried out at a temperature of 15 ° C (TCU A 6〇atm㈣ carbon monoxide for 3 hours) and then the reactor was cooled to room temperature. After analyzing the reaction solution, it was found that the conversion rate of butadiene was 85%, and the desired The selectivity of 3_penta vinegar is about 93%, and the selectivity to 2_penta vinegar is about 3.5% Si repeated reaction results shows that the catalytic activity of such catalyst selectivity and consistent.
505626 A7 B7 五 •、發明説明（5) 實施例3 : 再重複例2中的反應8次，以檢查此觸媒系 的穩定度，其結果顯示於表一。 表一 __ 統 反應編號 丁二烯轉化率 3-戊二烯酯的選擇性 92% 93% 94% 93% 4-戊二烯_1 選擇性 3.0% ---——« 3,6% 90% 94% 4.1% 4 90% 93% 3.1% (請先閲讀背面之注意事項再填寫本頁) 90% 95% 3.5% 91% 89% 88% 93% 92% 93% 3.4% 3.2% 3.5% 經濟部中央標準局員工消費合作社印製 一紙 比較例1 : 重複例1之步驟，除以〇.43g的1，4二苯基磷丁 烧（1 .0 8 m m ο 1)取代α，α’ -二苯基-鄰-二甲苯，以及利用 0.31g(1.89mmol)的 2,4,6-三甲基苯甲酸取代 2,4,6-三異丙基苯甲酸。反應是在溫度15〇°C以及60atm的 一氧化碳的環境下進行3小時。分析反應溶液後可 發現，丁二烯的轉換率為 94%，而對所要的 3-戊烯 酯之選擇性約為68%，對2-戊烯酯的選擇性約為 2 30/〇。 長尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 505626 A7 B7 五、發明説明（6 ) 比較例2 : (請先閲讀背面之注意事項再填寫本頁) 將比較例 1中所獲得之反應溶液以真空蒸餾法 去除揮發性物質。為了檢查觸媒系統的穩定度，2.1 g 的甲醇以及 5ml的丁二烯被加入反應器内，然後進 行重複的羰化反應。反應是在溫度150°C以及60atm 的一氧化碳的環境下進行3小時，然後將反應器冷 卻至室溫。分析反應溶液後可發現，丁二烯的轉換 率為85%，而對所要的3-戊烯酯之選擇性約為65%， 對2-戊烯酯的選擇性約為 19%。而經過氣相層析管 柱分析後，其結果亦顯示 2,4,6-三甲基苯甲酸酯的 形成（來自2,4,6-三甲基苯曱酸的酯化）。因此，苯曱 酸的總含量會隨反應而漸漸減少，使得羰化反應的 速率降低。 經濟部中央標準局員工消費合作社印製 爰此，根據本發明所提出之用以催化丁二烯酯 化反應以生成 3 _烯基戊酸酯類化合物之觸媒組合 物，其利用含巨大立體效應之官能基的苯甲酸，例 如2,4,6-三異丙基苯甲酸為共催化劑，以進行酯化 反應。經過實驗後，證實此類苯甲酸不會在酯化條 件下被醇類酯化，且重複使用後仍具有高催化活性， 不需額外增加此類酸基助觸媒，即可再加入丁二烯 及醇類，接著進行酯化反應，以生成3 -烯基戊酸酯 類化合物。由於此類苯甲酸無法進行酯化反應，因 此亦無需將被酯化之助觸媒加以回收、水解與再利 ____8_.____ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 505626 A7 B7 五、發明説明（7 ) 用，對於酯化反應製程及降低生產成本具有明顯的 功效。此外，利用本發明所提出之酯化反應觸媒， 其對3 -烯基戊酸酯之選擇性高，經過酯化反應後的 產物為純度> 97%之3-烯基戊酸酯。 雖然本發明已以較佳實施例揭露如上，然其並 非用以限定本發明，任何熟習此技藝者，在不脫離 本發明之精神和範圍内，當可作各種之更動與潤飾， 因此本發明之保護範圍當視後附之申請專利範圍所 界定者為準σ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）505626 A7 B7 V. Description of the invention (5) Example 3: The reaction in Example 2 was repeated 8 times to check the stability of the catalyst system. The results are shown in Table 1. Table 1 __ System reaction number Butadiene conversion rate 3-pentadienyl ester selectivity 92% 93% 94% 93% 4-pentadiene_1 selectivity 3.0% ------- «3,6% 90% 94% 4.1% 4 90% 93% 3.1% (Please read the notes on the back before filling out this page) 90% 95% 3.5% 91% 89% 88% 93% 92% 93% 3.4% 3.2% 3.5% A comparative example 1 printed by a staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: The procedure of Example 1 was repeated, and divided by 0.43 g of 1,4-diphenylphosphine (1.08 mm ο 1) instead of α, α '-Diphenyl-o-xylene, and 2,4,6-triisopropylbenzoic acid was replaced with 0.31 g (1.89 mmol) of 2,4,6-trimethylbenzoic acid. The reaction was carried out in an atmosphere of carbon monoxide at a temperature of 15 ° C and 60 atm for 3 hours. After analyzing the reaction solution, it was found that the conversion of butadiene was 94%, and the selectivity to the desired 3-pentenyl ester was about 68%, and the selectivity to 2-pentenyl ester was about 2 30/0. Long scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) 505626 A7 B7 V. Description of invention (6) Comparative example 2: (Please read the precautions on the back before filling this page) Will be obtained in comparative example 1 The reaction solution was subjected to vacuum distillation to remove volatile substances. In order to check the stability of the catalyst system, 2.1 g of methanol and 5 ml of butadiene were added to the reactor, and then repeated carbonylation reactions were performed. The reaction was carried out in an atmosphere of carbon monoxide at a temperature of 150 ° C and 60 atm for 3 hours, and then the reactor was cooled to room temperature. After analyzing the reaction solution, it was found that the conversion of butadiene was 85%, and the selectivity to the desired 3-pentenyl ester was about 65%, and the selectivity to 2-pentenyl ester was about 19%. After GC column analysis, the results also showed the formation of 2,4,6-trimethylbenzoate (from the esterification of 2,4,6-trimethylbenzoic acid). Therefore, the total content of phenylarsinic acid will gradually decrease with the reaction, resulting in a reduction in the rate of the carbonylation reaction. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, according to the present invention, a catalyst composition for catalyzing the butadiene esterification reaction to form a 3-alkenyl valerate compound is used, which uses a huge three-dimensional An effecting functional benzoic acid, such as 2,4,6-triisopropylbenzoic acid, is used as a co-catalyst for the esterification reaction. After experiments, it was confirmed that such benzoic acid will not be esterified by alcohols under esterification conditions, and still has high catalytic activity after repeated use. No additional acid-based catalysts can be added, but succinic acid can be added. Alkenes and alcohols are then esterified to form 3-alkenylvalerate compounds. Since this kind of benzoic acid cannot be esterified, there is no need to recover, hydrolyze and re-catalyze the esterified co-catalyst ____ 8 _.____ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 505626 A7 B7 V. Description of the invention (7) It has obvious effect on the esterification process and reducing the production cost. In addition, the esterification reaction catalyst proposed by the present invention has high selectivity to 3-alkenylvalerate, and the product after the esterification reaction is 3-alkenylvalerate with a purity > 97%. Although the present invention has been disclosed as above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and retouches without departing from the spirit and scope of the present invention. Therefore, the present invention The scope of protection shall be determined by the scope of the attached patent application. (Please read the precautions on the back before filling out this page.) Printed on the paper standard printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, the Chinese National Standard (CNS) Α4 specifications (210X297 mm)