200906789 九、發明說明 【發明所屬之技術領域】 本發明係關於一種高級醇丁烯酸酯的製造方法，特別 係關於作爲甘薯的重要害蟲甘藷蟻象（學名·· Cylas formicarius ( Fabricius))的性費洛蒙（Sex pheroinone) 成份 E-2-丁烯酸-Z-3-十二烯基酯（Z-3-dodecenyl-E-2-butenoate)的製造方法。 【先前技術】 通常，高級醇酯的製造方法公知爲： (1) 在鹼存在下’高級醇與羧酸反應（實驗化學講 座第4版22’ p50，1_2酯類，e.由酸酐的合成）； (2) 在鹼存在下’闻級醇與殘酸酿氯（carb〇xyIic acid chloride)反應（實驗化學講座第4版22，p50，1.2 酯類’ f_由氧齒化物（acid halognide compound)的合 成） (3) 高級醇與酯的酯交換反應（實驗化學講座第4 版22，p51，1.2酯類，h.酯交換反應）等。 【發明內容】 將上述公知的方法應用於高級醇丁烯酸酯的製造，考 慮了： (1A)於鹼存在下，高級醇與丁烯酸酐之反應； (2A)在驗存在下，筒級醇與巴丑醯氯（crotonyl -4- 200906789 chloride)之反應； (3A)高級醇與丁烯酸甲酯的酯交換反應等。 此外，丁烯酸也稱爲2-丁烯酸。 但是，於鹼性存在下進行（1A )及（2 A )的方法 中，反應中發生異構化作用，作爲不純物，生成高級醇的 3-丁烯酸酯。此外，在（3 A )的方法中，反應速度慢，工 業上製造高級醇丁烯酸酯需要很長時間，本身大量使用作 爲原料的丁烯酸酯產生的目的物非常少，並存在價格貴等 缺點。 美國專利4,732,756的說明書記載了係關於作爲甘藷 蟮象（學名：Cylas formicarius ( Fabricius))的亞種、 作爲性費洛蒙具有E-2-丁烯酸-Z-3-十二烯基酯的甘薯象 鼻蟲（Sweet Potato Weevil )(學名：Cylas formicarius elegantus)。此外，E_2_丁烯酸- Z- 3-十二烯基酯是用上述 (2 )的方法製造的，由於生成1 〇 %左右的3 - 丁烯酸酯副 產物，所以使用高速液相色譜法進行分離純化。 如此，要求於工業上高純度、且高產率地製造高級醇 丁烯酸酯的方法。尤其於合成作爲甘藷犠象的性費洛蒙成 份的E-2-丁烯酸-Z-3-十二烯基酯時，因爲將該化合物作 爲引誘劑使用，在工業上要求具有高純度、高產率。 本發明是鑒於上述情況進行的，目的爲提供一種解決 以往技術存在的問題、有效地製造高純度的高級醇丁烯酸 酯的方法。 爲了解決上述課題’對高級醇丁烯酸酯的製造方法進 -5- 200906789 行硏究的結果，藉由使用對甲苯磺酸作爲催化劑’使高級 醇與丁烯酸進行脫水反應’可以控制作爲副產物的高級醇 的3 -丁烯酸酯的生成不足0.5%。此外，發現藉由使用精 餾塔將反應中生成的水與作爲溶劑的甲苯共沸除去，可使 反應有效地進行，發現以高純度製造高級醇丁烯酸酯，完 成了本發明。 因此，本發明提供一種高級醇丁烯酸酯的製造方法， 所述方法包括使丁烯酸與碳數爲6〜20的高級一元醇於芳 香族烴類有機溶劑或鹵素類有機溶劑中，於酸催化劑的存 在下，進行脫水反應。作爲較佳的實施方式之一，包括藉 由蒸餾塔將於上述脫水反應中生成的水與芳香族烴類有機 溶劑共沸除去。 藉由使用本發明的方法，可於工業上高純度且高產率 地製造高純度的高級醇丁烯酸酯。 用以實施本發明之最佳形態 本發明的高級醇丁烯酸酯的製造方法爲使碳數爲6〜 2 0的高級一元醇與丁烯酸進行脫水酯化。 作爲碳數6〜20的高級一元醇，例如具有直鏈或側鏈 的脂肪族醇或環狀醇。具體地，例如用於製造甘藷蟻象性 費洛蒙成份的Z-3-十二碳烯醇。 對於每1 m ο 1高級一元醇，丁烯酸最佳爲1 · 2〜1 .4 mol。 本發明將高級一元醇與丁烯酸、作爲催化劑的對甲苯 -6- 200906789 磺酸、作爲溶劑的甲苯放入反應體系，最佳於11 0〜13 〇 °c (迴流溫度）下反應8小時左右’得到目的物高級醇丁烯 酸酯。此外，最佳使用蒸餾塔將反應生成的水與甲苯共沸 蒸餾除去，使反應良好地進行。 作爲本發明使用的溶劑’除了甲苯、苯等芳香族烴類 有機溶劑外，例如二氯乙烷、二氯甲烷等鹵素類有機溶 劑，特別最佳爲甲苯。 對於每1 mol高級醇，溶劑量最佳使用300g〜500g。 作爲該脫水酯化反應的催化劑’可使用硫酸、鹽酸等 無機酸或芳香族磺酸等有機酸’特別最佳爲對甲苯磺酸。 對於每1 mol高級醇，催化劑量最佳使用0.1〜〇·5 mol。 爲了使溶劑迴流，反應溫度最好於所使用溶劑的沸點 以上進行反應，當使用甲苯作爲溶劑時，反應溫度最佳爲 1 1 0〜1 3 0°c。該反應通常於氮氣等惰性氣體的氣氛下進 行。 藉由本發明得到的高級醇丁烯酸酯，作爲異構體的3 -丁烯酸酯的含量不足〇 · 5 %，最佳於0.1 %以下，可以高純 度且高產率地製造高級醇丁烯酸酯。 【實施方式】 依據實施例和比較例對本發明的具體方式進行說明’ 但本發明並不限於下述的實施例。 200906789 實施例1 將 1 14.57g ( 0.60 mol ) Z-3-十二碳烯醇、67_83g (0.78 mol) 丁 嫌酸、1.14g( 6.00 mmol)對甲苯磺酸、 2 00g甲苯放入附有攪拌機、冷卻器、蒸餾塔、分餾管、溫 度計的500 ml四口燒瓶中，一邊攪拌一邊升溫至°C。 攪拌2小時後，從塔頂逐漸地餾去迴流的甲苯/水共沸 物，此時餾出液的溫度爲8 5 °C。8小時後，不再有水餾 出，將餾出液的溫度升至1131，反應結束。此時藉由氣 相色譜法的面積％求得轉化爲酯的轉化率爲99.8% ’作爲 副產物的3-丁烯酸酯含量爲0·08%。 將得到的反應液冷卻到3 0 °C以下，用1 0 〇 g水、接著 用1 0 0 g 1 0 %的N aH C Ο 3水溶液洗淨後，減壓除去甲苯。藉 由將濃縮液減壓蒸餾純化得到139.29g ( 0.55 mol ’產率： 9 0.9 3 %，純度：9 8.8 5 % )的目的物E - 2 - 丁烯酸-Z - 3 -十二 烯基酯。 比較例1在鹼存在下，高級醇與丁烯酸酐的反應 將189.30g ( 1.00 mol) Z-3-十二碳烯醇放入附有攪拌 機、冷卻器、溫度計的2L四口燒瓶中，在20°C攪拌。花 費3小時的時間在3〜4 0 °C對其中滴加另外調製的甲基氯 化鎂的四氫呋喃溶液406.30g ( 1.05 mol)。其後’升溫至 7 0 °C攪拌1小時。攪拌後’將該反應液冷卻到3 0 °C ’加入 5 5 9 g四氫呋喃後，花費1.5小時的時間在3 0〜4 0 °C滴加 1 6 5 · 0 0 g ( 1 . 0 7 m ο 1 )的丁烯酸酐。結束滴加後，將反應液 200906789 在40°C下攪拌2小時，藉由420g水終止反應。 反應後’用氣相色譜法的面積％求得轉化爲酯的轉化 率爲9 6.5 % ’作爲副產物的3 - 丁儲酸酯含量爲丨.8 9 %。將 反應液減壓除去四氫呋喃後’藉由將濃縮液減壓蒸餾純化 得至[1 204.55g ( 0.79 mol，產率：79.78%，純度： 97.20%)的目的物E-2-丁烯酸-Z-3-十二烯基酯。 比較例2在鹼存在下’高級醇與巴豆醯氯（cr〇t〇nyl chloride)的反應 將 19.09g(0.10 mol) Z-3 -十二碳烯醇、7.91g(0.10 mol )吡啶、1 00g正己烷放入附有攪拌機、冷卻器、溫度 計的3 0 0 ml四口燒瓶中，在l〇°C攪拌。花費1小時的時 間在10〜15 °C對其中滴加12.20g (0.105 mol)的巴豆醯 氯（cro tony 1 chloride )的正己烷溶液 20g。滴加後，在 2 0〜3 0 °C攪拌反應液1小時，使用5 2 g的5 %的N aO Η水溶 液終止反應。此時，用氣相色譜法的面積％求得轉化爲酯 的轉化率爲9 7.7 %，作爲副產物的3 - 丁烯酸酯含量爲 2 3 4 %。將得到的反應液使用5 0 g水洗淨兩次’減壓除去 正己烷’藉由減壓蒸餾純化得到20.51g( 0.079 mol’產 率：78.53°/。，純度：96.62%)的目的物 E-2 -丁嫌酸-Z-3-十二烯基酯。 比較例3高級醇與丁烯酸甲酯的酯交換反應 將 38.19g ( 〇·2〇 m〇1) z_3-十二碳烯醇、28.60g ( 0.29 200906789 mol ) 丁烯酸甲酯、作爲催化劑的0_76g ( 4.0 苯磺酸、120g甲苯放入附有攪拌機、冷卻器 餾管、溫度計的 500 ml四口燒瓶中，在] 拌。使用蒸餾塔將反應中生成的甲醇作爲與E 除去。經過1 8〜2 0小時，不再有甲醇餾出 卻至30°C，使用150g水終止反應。此時，目 法的面積％求得轉化爲酯的轉化率爲98.1% 的3 - 丁烯酸酯含量爲0.5 0 %。 將得到的反應液減壓除去甲苯。藉由減H 到 4 5 · 5 5 g ( 0 1 8 m ο 1，產率：8 8.9 7 %，純度 目的物E-2-丁烯酸-Z-3-十二烯基酯。 mmol )對甲 、蒸餾塔、分 .1 0 〜11 5 °C 攪 戸苯的混合物 ，將反應液冷 奢由氣相色譜 1作爲副產物 适蒸餾純化得 :9 8.5 9 % )的 -10-200906789 IX. OBJECTS OF THE INVENTION [Technical Field] The present invention relates to a method for producing a higher alcohol crotonate, and more particularly to the sex of a sweet potato ant elephant (scientific name Cylas formicarius ( Fabricius)) which is an important pest of sweet potato. Sex pheroinone A method for producing a component Z-2-dodecenyl-E-2-butenoate. [Prior Art] In general, a method for producing a higher alcohol ester is known as: (1) Reaction of a higher alcohol with a carboxylic acid in the presence of a base (Experimental Chemistry Lecture 4th Edition 22' p50, 1_2 ester, e. Synthesis from an acid anhydride (2) In the presence of a base, the reaction of sulphuric acid with carb〇xyIic acid chloride (Experimental Chemistry Lecture 4th edition 22, p50, 1.2 esters f_ by acid halognide Synthesis of compound) (3) Transesterification of higher alcohols and esters (Experimental Chemistry Lecture 4th edition 22, p51, 1.2 esters, h. transesterification reaction). SUMMARY OF THE INVENTION The above-mentioned known method is applied to the production of higher alcohol crotonate, and it is considered that: (1A) the reaction of higher alcohol with butenoic anhydride in the presence of a base; (2A) in the presence of a test tube The reaction of alcohol with crotonyl -4- 200906789 chloride; (3A) transesterification of higher alcohol with methyl crotonate. Further, crotonic acid is also known as 2-butenoic acid. However, in the method of carrying out (1A) and (2A) in the presence of a basicity, isomerization occurs in the reaction, and as a impurity, a 3-butenoate of a higher alcohol is produced. Further, in the method of (3 A), the reaction rate is slow, industrial production of a higher alcohol crotonate takes a long time, and the use of a large amount of crotonate as a raw material by itself is very small, and it is expensive. And so on. The specification of U.S. Patent No. 4,732,756 describes a subspecies of the genus philaea (Cylas formicarius ( Fabricius)) as a pheromone having an E-2-butenoic acid-Z-3-dodecenyl ester. Sweet Potato Weevil (scientific name: Cylas formicarius elegantus). Further, E_2-butenoic acid-Z- 3-dodecenyl ester is produced by the method of the above (2), and high-performance liquid chromatography is used because a by-product of methacrylate is formed in an amount of about 1% by weight. The method is isolated and purified. Thus, a method of producing a higher alcohol crotonate in a high purity and high yield in the industry is required. In particular, when synthesizing E-2-butenoic acid-Z-3-dodecenyl ester as a pheromone component of sweet potato, since it is used as an attractant, it is industrially required to have high purity. High yield. The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for efficiently producing a high-purity higher alcohol crotonic acid ester which solves the problems of the prior art. In order to solve the above problem, as a result of the investigation of the method for producing higher alcohol crotonate, the use of p-toluenesulfonic acid as a catalyst to dehydrate a higher alcohol with butenoic acid can be controlled as The formation of the 3-butenoate of the higher alcohol as a by-product is less than 0.5%. Further, it has been found that the reaction can be efficiently carried out by azeotropically removing water formed in the reaction with toluene as a solvent by using a rectification column, and it has been found that the higher alcohol crotonate is produced in high purity, and the present invention has been completed. Accordingly, the present invention provides a process for producing a higher alcohol crotonate, which comprises reacting crotonic acid with a higher monohydric alcohol having a carbon number of 6 to 20 in an aromatic hydrocarbon organic solvent or a halogen organic solvent. The dehydration reaction is carried out in the presence of an acid catalyst. As one preferred embodiment, water which is formed in the above dehydration reaction by a distillation column is azeotropically removed with an aromatic hydrocarbon organic solvent. By using the method of the present invention, high-purity higher alcohol crotonate can be produced industrially in high purity and high yield. BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a higher alcohol crotonate of the present invention is to dehydrate esterify a higher monohydric alcohol having a carbon number of 6 to 20 with butenoic acid. As the higher monohydric alcohol having 6 to 20 carbon atoms, for example, an aliphatic alcohol or a cyclic alcohol having a linear or side chain. Specifically, for example, Z-3-dodecanol used for the production of a sweet potato ant-like pheromone component. For every 1 m ο 1 higher monohydric alcohol, the crotonic acid is preferably from 1 · 2 to 1.4 mol. In the present invention, a higher monohydric alcohol and a crotonic acid, a p-toluene-6-200906789 sulfonic acid as a catalyst, and a toluene as a solvent are placed in the reaction system, and the reaction is preferably carried out at a temperature of 11 0 to 13 ° C (reflow temperature) for 8 hours. Left and right 'obtained the target higher alcohol butenoate. Further, the water produced by the reaction is preferably azeotropically distilled off with toluene using a distillation column to carry out the reaction well. The solvent used in the present invention is, in addition to an aromatic hydrocarbon organic solvent such as toluene or benzene, for example, a halogen-based organic solvent such as dichloroethane or dichloromethane, and particularly preferably toluene. For each 1 mol of the higher alcohol, the solvent amount is preferably from 300 g to 500 g. As the catalyst for the dehydration esterification reaction, an organic acid such as sulfuric acid or hydrochloric acid or an organic acid such as an aromatic sulfonic acid can be used, and p-toluenesulfonic acid is particularly preferable. For each 1 mol of higher alcohol, the catalyst amount is preferably 0.1 to 〇·5 mol. In order to reflux the solvent, the reaction temperature is preferably carried out above the boiling point of the solvent to be used. When toluene is used as the solvent, the reaction temperature is preferably from 1 10 to 1 30 °c. This reaction is usually carried out under an atmosphere of an inert gas such as nitrogen. The higher alcohol crotonate obtained by the present invention has a content of a 3-butenoic acid ester as an isomer of less than 5%, preferably less than 0.1%, and can produce a higher alcohol butene at a high purity and a high yield. Acid ester. [Embodiment] Specific embodiments of the present invention will be described based on the embodiments and comparative examples. However, the present invention is not limited to the embodiments described below. 200906789 Example 1 1 14.57 g (0.60 mol) Z-3-dodecenol, 67-83 g (0.78 mol) of butyl acid, 1.14 g (6.00 mmol) of p-toluenesulfonic acid, 200 g of toluene were placed in a mixer In a 500 ml four-necked flask of a cooler, a distillation column, a fractionation tube, and a thermometer, the temperature was raised to ° C while stirring. After stirring for 2 hours, the refluxing toluene/water azeotrope was gradually distilled off from the top of the column, at which time the temperature of the distillate was 85 °C. After 8 hours, no more water was distilled off, and the temperature of the distillate was raised to 1,131, and the reaction was completed. At this time, the conversion ratio of the conversion to the ester was 99.8% by the area % of the gas phase chromatography, and the content of the 3-butenoate as a by-product was 0.08%. The obtained reaction liquid was cooled to 30 ° C or lower, washed with 10 g of water, followed by 100 g of a 10% aqueous solution of NaH C Ο 3, and then toluene was removed under reduced pressure. Purification by distillation under reduced pressure gave 139.29 g (0.55 mol yield: 9 0.9 3 %, purity: 9 8.8 5 %) of the desired product E 2 -butenoic acid-Z 3 - dodecenyl group ester. Comparative Example 1 Reaction of Higher Alcohol with Butenoic Anhydride in the Presence of a Base 189.30 g (1.00 mol) of Z-3-dodecenol was placed in a 2 L four-necked flask equipped with a stirrer, a cooler, and a thermometer. Stir at 20 °C. A solution of 406.30 g (1.05 mol) of a separately prepared methylmagnesium chloride tetrahydrofuran solution was added dropwise at 3 to 40 ° C over a period of 3 hours. Thereafter, the temperature was raised to 70 ° C and stirred for 1 hour. After stirring, the reaction solution was cooled to 30 ° C. After adding 5 5 9 g of tetrahydrofuran, it took 1.5 hours to add 1 6 5 · 0 0 g (1.07 m) at 30 to 40 °C. ο 1 ) of butenoic anhydride. After the completion of the dropwise addition, the reaction liquid 200906789 was stirred at 40 ° C for 2 hours, and the reaction was terminated by 420 g of water. After the reaction, the conversion ratio of the ester converted to the ester was determined to be 96.5 % by the area % of the gas chromatography, and the content of the 3-butyrate as a by-product was 8.99%. After the reaction liquid was removed under reduced pressure of tetrahydrofuran, the residue was purified by distillation under reduced pressure to yield [1 204.55 g (0.79 mol, yield: 79.78%, purity: 97.20%). Z-3-dodecenyl ester. Comparative Example 2 The reaction of a higher alcohol with cr〇t〇nyl chloride in the presence of a base would give 19.09 g (0.10 mol) of Z-3 -dodecenyl alcohol, 7.91 g (0.10 mol) of pyridine, 1 00 g of n-hexane was placed in a 300 ml four-necked flask equipped with a stirrer, a cooler, and a thermometer, and stirred at 10 ° C. It took 1 hour to add 20 g of a solution of 12.20 g (0.105 mol) of cro tony 1 chloride in n-hexane at 10 to 15 °C. After the dropwise addition, the reaction solution was stirred at 20 to 30 ° C for 1 hour, and the reaction was terminated with 5 2 g of a 5% aqueous solution of Na 2 O. At this time, the conversion ratio of the ester to the ester was determined by the area % of the gas chromatography to be 9.77%, and the content of the 3-butenoate as a by-product was 234%. The obtained reaction liquid was washed twice with 50 g of water to remove n-hexane under reduced pressure, and purified by distillation under reduced pressure to give 20.51 g (yield: 0.079 mol, yield: 78.53 °, purity: 96.62%). E-2 - butyl acid-Z-3-dodecenyl ester. Comparative Example 3 Transesterification of higher alcohol with methyl crotonate 38.19 g (〇·2〇m〇1) z_3-dodecenol, 28.60 g (0.29 200906789 mol) of methyl crotonate as catalyst 0_76g (4.0 benzenesulfonic acid, 120g of toluene was placed in a 500 ml four-necked flask equipped with a stirrer, a cooler tube, and a thermometer, and mixed). The methanol produced in the reaction was removed as E with a distillation column. 8 to 20 hours, no more methanol was distilled off to 30 ° C, and the reaction was terminated with 150 g of water. At this time, the area % of the mesh method was found to be converted to an ester conversion rate of 98.1% of 3-butenoate. The content is 0.5% by weight. The obtained reaction solution is decompressed to remove toluene by subtracting H to 4 5 · 5 5 g (0 1 8 m ο 1, yield: 8 8.9 7 %, purity target E-2- Butyl-Z-3-dodecenyl ester. mmol) A mixture of a benzene, a distillation column, and a dispersion of .10 to 11 5 ° C. The reaction liquid is cooled by gas chromatography 1 as a by-product. Purified by distillation: 9 8.5 9 % ) -10-