200418753 玖、發明說明： 【發明所屬之技術領域】 本發明係關於在聚醯胺改質劑、聚酯改質劑、化妝品基 劑、聚酯或聚醯胺之原料等之用途上有用之分歧己二酸之製 造方法。 【先前技術】 向來所知之分歧己二酸之製造方法爲以下①、②方法， ① 2,5 -二乙基己二酸之製造方法爲，將1,3 -丁二烯與金屬鈉 於二甲基醚中，於-70 °C反應後，依次與溴化鎂及二氧化碳 反應，得到目的物2, 5 -二乙基己二酸之製造方法爲已知（參 閱專利文獻1 )。 ② 2,5 -二甲基己二酸之製造方法爲，使用過氧化二第三丁基 等之過氧化物作爲觸媒，將η-壬烷、丙酸與乙炔於120°C反 應，得到目的物2，5 -二甲基己二酸之製造方法爲已知（參閱 專利文獻1 )。 惟，使用①2, 5 -二乙基己二酸之製造方法時，其使用金屬 鈉，此種化合物具自然發火性，有與水反應之爆發等性質之 安全上問題。 再者，使用②2, 5 -二甲基己二酸之製造方法時，具有加 熱、衝擊等爆發性質之過氧化物及與空氣或氧之混合而具有 廣泛之爆發界限上之安全性問題。 由以上所述’此2方法作爲工業上之製造方法並非實用、 令人滿意之方法。 [專利文獻1 ] 200418753 美國專利第3 3 7 5 272號說明書 [專利文獻2 ] 美國專利第3 5 4 9 6 9 7號說明書 【發明內容】 發明欲解決之課題 本發明之目的係提供分歧己二酸之工業上適合之製造方 法。 解決課題之手段200418753 发明 Description of the invention: [Technical field to which the invention belongs] The present invention is divided on the usefulness of polyamine modifiers, polyester modifiers, cosmetic bases, raw materials for polyesters or polyamides, etc. Method for producing adipic acid. [Prior art] The conventionally known methods for producing adipic acid are the following methods ① and ②, and ① The method for producing 2,5-diethyl adipate is to combine 1,3-butadiene with sodium metal in The dimethyl ether is reacted at -70 ° C, and then reacted with magnesium bromide and carbon dioxide in order to obtain the target 2,5-diethyladipic acid (see Patent Document 1). ② The method for producing 2,5 -dimethyladipate is to use a peroxide such as di-tert-butyl peroxide as a catalyst, and react η-nonane, propionic acid and acetylene at 120 ° C to obtain A method for producing the target 2,5-dimethyladipate is known (see Patent Document 1). However, when using ① 2,5-diethyl adipate production method, it uses sodium metal. This compound has natural pyrophoric properties and has safety issues such as the reaction with water and the outbreak. In addition, when using the method for producing 2,5-dimethyl adipate, peroxides having explosive properties such as heating and impact, and mixtures with air or oxygen have safety issues on a wide range of explosive boundaries. As mentioned above, these two methods are not practical and satisfactory as industrial production methods. [Patent Document 1] 200418753 US Patent No. 3 3 7 5 272 [Patent Document 2] US Patent No. 3 5 4 9 6 9 7 [Summary of the Invention] Problem to be Solved by the Invention The object of the present invention is to provide divergence. Industrially suitable manufacturing method for diacid. Solutions to problems
本發明提供以下（1 )〜（3 )。 (1) 一種一般式（II)所示分歧己二酸之製造方法， R1 R2 } I R4 R6 ! I I 1 HOOC — C—C | | 1 1 C-C一 | I -COO Η 1 L H R3 R5 Η (Π) (式中，Ri、R2、R3、R4、R5及R6同下歹[j之定義） 其特徵係包含將式（I )所示化合物 R2 R3The present invention provides the following (1) to (3). (1) A method for producing bifuric adipic acid represented by general formula (II), R1 R2} I R4 R6! II 1 HOOC — C—C | | 1 1 CC 一 | I -COO Η 1 LH R3 R5 Η ( Π) (In the formula, Ri, R2, R3, R4, R5, and R6 are the same as the following definition of [j]. Its characteristics include compound R2 R3 represented by formula (I)
或相異爲氫原子或 (式中，R1、R2、R3、R4、R5 及 R6 相同 院基，R7爲甲醯基或羥基甲基，其中 表示爲單鍵或雙鍵，惟，R1、R2、R3、^ R、R5及R6中至少 200418753 一者爲院基）’於驗金屬或驗土金屬之氫氧化物存在下反 應之步驟。 (2) 如上述（1)所述分歧己二酸之製造方法，其中…及 R6爲烷基，R2、R3、R4及R5爲氫原子。 (3) 如上述（1)或（2)所述分歧己二酸之製造方法，其 中鹼金屬或鹼土金屬之氫氧化物爲氫氧化鈉或氫氧化_。 以下，一般式（I )所示化合物爲化合物（I )，一般式（11 )戶斤 示分歧己二酸爲化合物（I I )之表現。 發明實施之形態 一般式中各基之定義，烷基例如爲碳數1〜10之直鏈或分 歧狀烷基，其具體例爲甲基、乙基、丙基、異丙基、丁基、 異丁基、第二丁基、第三丁基、戊基、己基、庚基、辛基、 壬基、癸基等，其中以甲基或乙基爲宜。 本發明製造方法之原料爲化合物（I )，其可以公知之方法 (美國專利第2 9 1 05 20號等）或其依據之方法，例如環化丙 烯醛衍生物，或者，於必要時，可將所得二氫尅喃衍生物之 氫還原而得到。 鹼金屬或鹼土金屬之氫氧化物爲氫氧化鉀、氫氧化鈉、氫 氧化鎂、氫氧化鈣等，其中，可單獨或合倂2種以上使用。 鹼金屬或鹼土金屬之氫氧化物，相對於化合物（I) 1莫耳，宜 爲1.5莫耳以上’更宜爲1.5〜5·0莫耳，再者，ι·8〜30莫耳 爲更宜。 本發明之製造方法中，反應溫度爲200〜320 °C爲宜，更宜 爲200〜250°C，進一步以220〜250。(：爲較宜。 200418753 此反應爲常壓或加壓條件下，宜爲2.0MPa以下，更宜爲 l.OMPa以下進行。 反應時間未特別限定，5小時以上爲宜，5〜20小時爲更宜。 反應中’可使用反應溶劑，該反應溶劑若不影饗反應，則 未特別限定，該反應溶劑可列舉例如爲二玩基_等之酸溶 劑、流動石蠟等之烴系溶劑等，可混合此等溶劑使用。反應 溶劑之使用量未特別限定，相對於化合物（I)，宜爲5〇〜2〇〇 重量％，更宜爲70〜150重量％。 又，作爲反應時間之縮短或產率之提升之目的，進行氧化 鋅或氧化銅等金屬氧化物等觸媒之添加反應，該觸媒之使用 量，相對於化合物（I)，以0.1〜5重量％爲宜。 反應後，化合物（II)以驗金屬或鹼土金屬之鹽之形態得 到，但，其中如加入硫酸、鹽酸等水溶液等，可得到化合物 (II) 0 又，所得之化合物（II)，爲使其純度提升，由反應液等交 付提取、晶析、蒸餾等之純化操作爲宜。 本發明之製造方法爲簡易、廉價、安全性上亦優之工業上 適合之製造方法。 化合物（Π)於聚醯胺改質劑、聚酯改質劑、化妝品基劑、 聚酯或聚醯胺之原料等之用途上爲有用者。 【實施方式】 實施例1 : 2，5 -二乙基己二酸之合成 170.0g( 1.〇111〇1)2,5-二乙基-3,4-二氫-21^-尅喃-2-甲醇、 170.0g( 2.4m〇l )氫氧化鈉（關東化學股份有限公司）及200g -10- 200418753 流動石蠟60S (中央化成股份有限公司）於裝備有還流器、 · 壓力控制及溫度控制可能之電熱爐之1 L鎳製高壓鍋中，以 1 .OMPa以下加熱攪拌。以氣體測量器測定產生之氫氣，一 邊檢測反應之進行，一邊於220〜230°C，反應10小時。反 應後，將含有2，5 -二乙基己二酸二鈉鹽之反應液冷卻至1 00 °C以下，於400g蒸餾水中溶解，再滴入30%硫酸420g而濾 取析出粗製之2，5 -二乙基己二酸。所得之粗製2，5 -二乙基 己二酸溶解於3 00ml甲基異丁基酮中、水洗後，於60°C減壓 濃縮得到含1 8 3 g之2，5 -二乙基己二酸殘渣。由此殘渣以η · ^ 己烷結晶化，得到170g之2, 5-二乙基己二酸之白色結晶（產 率8 5% )，所得之2 , 5 ·二乙基己二酸之物性以下列所示。 〗H-NMR ( 400MHz，CDCls , TMS ) 5 ( ppm ) : 0.90 ( t，6H)， 1.48-1.63(m，8H)， 2.23-2.25 (m，2H)， 13C-NMR ( 100MHz，CDCh，TMS ) (5 (ppm) : 11.92，25.81， 30 . 3 8 , 47 . 55 , 1 77.23 GC-MS ( Cl ):(誘導爲二甲基酯體後，分析） 保持時間 8.50 分鐘（m/z) : 230 (M+1) ^ 保持時間8_60分鐘（m/z) : 2 3 0 ( M+1) GC-MS分析條件及二甲基酯體之調製法 管柱··毛細管管柱 CP-Wax58 ( FFAP) CB ( GL Saiensu 公司 製）（25mx0.2//m)Or is a hydrogen atom or (wherein R1, R2, R3, R4, R5, and R6 are the same group, R7 is a methyl group or a hydroxymethyl group, which is represented by a single or double bond, but R1, R2 At least one of R3, R3, R5, R5, and R6 is 200418753.) The step of reacting in the presence of the hydroxide of the test metal or earth test metal. (2) The method for producing bifurcate adipic acid as described in (1) above, wherein ... and R6 are alkyl groups, and R2, R3, R4 and R5 are hydrogen atoms. (3) The method for producing bifurcate adipic acid as described in (1) or (2) above, wherein the hydroxide of the alkali metal or alkaline earth metal is sodium hydroxide or hydroxide. Hereinafter, the compound represented by the general formula (I) is the compound (I), and the general formula (11) shows the appearance of the adipic acid as the compound (I I). The definition of each group in the general formula of the embodiment of the invention. The alkyl group is, for example, a linear or branched alkyl group having 1 to 10 carbon atoms. Specific examples are methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, second butyl, third butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., among which methyl or ethyl is preferred. The raw material for the production method of the present invention is the compound (I), which can be a known method (US Patent No. 2 9 1 05 20, etc.) or a method based thereon, such as a cyclized acrolein derivative, or, if necessary, The obtained dihydrogran derivative is reduced by hydrogen. The hydroxides of the alkali metal or alkaline earth metal are potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, and the like. Among them, two or more kinds can be used alone or in combination. The hydroxide of the alkali metal or alkaline earth metal is preferably 1.5 mol or more relative to 1 mol of the compound (I), more preferably 1.5 to 5.0 mol, and more preferably ι 8 to 30 mol. should. In the manufacturing method of the present invention, the reaction temperature is preferably 200 to 320 ° C, more preferably 200 to 250 ° C, and further 220 to 250. (: Is more suitable.) 200418753 This reaction is carried out under normal pressure or pressure, preferably 2.0 MPa or less, and more preferably 1.0 MPa or less. The reaction time is not particularly limited, preferably 5 hours or more, 5 to 20 hours. In the reaction, a reaction solvent may be used, and the reaction solvent is not particularly limited as long as it does not affect the reaction. Examples of the reaction solvent include acid solvents such as dioxo, hydrocarbon solvents such as flowing paraffin, and the like. These solvents can be mixed and used. The amount of the reaction solvent used is not particularly limited, and it is preferably 50 to 200% by weight, and more preferably 70 to 150% by weight relative to the compound (I). In addition, as the reaction time is shortened For the purpose of improving the yield or the productivity, a catalyst for adding a metal oxide such as zinc oxide or copper oxide is reacted, and the amount of the catalyst used is preferably 0.1 to 5% by weight relative to the compound (I). The compound (II) is obtained in the form of a test metal or alkaline earth metal salt. However, if an aqueous solution such as sulfuric acid or hydrochloric acid is added to the compound (II), the compound (II) can be obtained in order to improve the purity , By the reaction solution Purification operations such as extraction, crystallization, distillation, etc. are suitable. The production method of the present invention is an industrially suitable production method that is simple, cheap, and excellent in safety. Compound (Π) is used in polyamine modifier, polymer It is useful for ester modifiers, cosmetic bases, raw materials of polyesters or polyamides, etc. [Embodiment] Example 1: Synthesis of 2,5-diethyl adipic acid 170.0 g (1. 〇111〇1) 2,5-diethyl-3,4-dihydro-21 ^ -gran-2-methanol, 170.0 g (2.4 ml) sodium hydroxide (Kanto Chemical Co., Ltd.) and 200 g -10- 200418753 Flowing paraffin 60S (Central Chemical Co., Ltd.) In a 1 L nickel pressure cooker equipped with a recirculator, an electric heating furnace with pressure control and temperature control possible, heat and stir at a pressure of 1.0 MPa or less. Use a gas measuring device The generated hydrogen gas was measured, and the reaction progressed at 220-230 ° C for 10 hours while detecting the progress of the reaction. After the reaction, the reaction solution containing 2,5-diethyl adipate disodium salt was cooled to 100 ° C In the following, it was dissolved in 400 g of distilled water, and 420 g of 30% sulfuric acid was added dropwise to filter out the crude 2,5-diethylhexane. Diacid. The obtained crude 2,5-diethyl adipic acid was dissolved in 300 ml of methyl isobutyl ketone, washed with water, and concentrated under reduced pressure at 60 ° C to obtain 2,5 -di Ethyl adipate residue. The residue was crystallized from η · ^ hexane to obtain 170 g of white crystals of 2,5-diethyladipate (yield: 8 5%). The physical properties of ethyl adipic acid are shown below: [H-NMR (400MHz, CDCls, TMS) 5 (ppm): 0.90 (t, 6H), 1.48-1.63 (m, 8H), 2.23-2.25 (m, 2H), 13C-NMR (100MHz, CDCh, TMS) (5 (ppm): 11.92, 25.81, 30.38, 47.55, 1 77.23 GC-MS (Cl): (after induction into dimethyl esters , Analysis) Hold time 8.50 minutes (m / z): 230 (M + 1) ^ Hold time 8_60 minutes (m / z): 2 3 0 (M + 1) GC-MS analysis conditions and the dimethyl ester Modulation column ·· Capillary column CP-Wax58 (FFAP) CB (made by GL Saiensu) (25mx0.2 // m)
管柱溫度：於100°C保持1分鐘後，以8°C /分鐘昇溫至270 °CColumn temperature: After holding at 100 ° C for 1 minute, increase the temperature to 270 ° C at 8 ° C / minute
注入溫度：2 7 0 °C -11- 200418753 檢出器溫度：28(TC 胃 將樣品溶解於苯/甲醇（3 / 7容量/容量）溶液中後，於室 溫30分鐘間加入三甲基矽烷基二重氮甲烷，攪拌，調製出 二甲基酯體溶液。 實施例2: 2, 5_二乙基己二酸之合成 除變更原料爲172.0g(1.0m〇l) 2,5-二乙基四氫趙喃_2-甲醇、99.0g ( 3.0mol )氫氧化鉀（關東化學股份有限公司） 及200g流動石鱲60S (中央化成股份有限公司）外，進行 以實施例1之相同操作，得到白色結晶之2，5 -二乙基己二酸 方 158g (產率 79%)。 實施例3: 2, 5 -二乙基己二酸之合成 除變更原料爲 168.0g( l.Omol ) 2 , 5-二乙基-3，4-二氫- 2H-趙喃-2-簾醛、99.0g(3.0mol)氫氧化紳（關東化學股份有 限公司）及200g流動石蠟60S (中央化成股份有限公司） 外，進行以實施例1之相同操作，得到白色結晶之2，5 -二乙 基己二酸131g (產率65%)。 參考例1: 2 ,5-二乙基-3, 4-二氫-2H-尅喃-2-羰醛之合成 _ 將攪拌片放入內容積100ml之壓力鍋中加入50g之2-乙基 丙烯醛（Aldrich公司製，純度85%)，於150〜160°C反應8 小時，其次，將反應液減壓餾除，82〜841 /50Pa之餾分得到 2,5-二乙基-3,4-二氫-2H-尅喃-2·羰醛 36.8g(產率 87%)。 參考例2: 2, 5 -二乙基四氫尅喃-2-甲醇之合成 將攪拌片放入內容積l〇〇ml之壓力鍋中加入10.0g之2,5-二乙基-3，4 -二氫-2H -尅喃-2 -羰醛及0 . 3 g海綿鎳觸媒（曰 -12- 200418753 揮化學股份有限公司製N - 1 1 3 )，於氫氣壓2 . 〇 Μ P a，溫度1 5 0 · °C反應6小時。反應終了後，由反應液濾除海綿鎳觸媒，得 到之濾液交付砂膠管柱色層分析[溶劑：n _己院/乙酸乙酯 =9/1(容量比）]’而得到2,5 -二乙基四氫尅喃-2-甲醇9.8g (產率98%)。 參考例3: 2, 5-二乙基-3, 4 -二氫-2H-尅喃-2-甲醇之合成 將攪拌片放入內容積10 0m 1之壓力鍋中加入〗〇.〇£之2, 5-二乙基- 3,4-二氫-2H-尅喃-2-羰醛及〇.5g之Cu-Cr系觸媒 (}^1^}^%製，0202?)，氫氣壓2.(^?3，於130。(：反應5 0 小時，反應終了後，由反應液濾除Cu - C r系觸媒，得到之濾 液交付矽膠管柱色層分析[溶劑：η -己烷/乙酸乙酯=9 / 1 (容 量比）]，而得到2,5_二乙基- 3,4·二氫- 2Η -尅喃-2-甲醇9.6g (產率9 5 % )。 發明之效果 依據本發明，提供於聚醯胺改質劑、聚酯改質劑、化妝品 基劑、聚酯或聚醯胺之原料等之用途上有用分歧己二酸之工 業上合適之製造方法。 · -13-Injection temperature: 2 7 0 ° C -11- 200418753 Detector temperature: 28 (TC stomach dissolves the sample in a benzene / methanol (3/7 capacity / volume) solution, and then adds trimethyl ether at room temperature for 30 minutes Silyl diazomethane was stirred to prepare a dimethyl ester solution. Example 2: Synthesis of 2, 5-diethyl adipate. The raw material was changed to 172.0 g (1.0 ml) 2,5- Diethyltetrahydrozhaonan_2-methanol, 99.0 g (3.0 mol) of potassium hydroxide (Kanto Chemical Co., Ltd.) and 200 g of flow stone 60S (Central Chemical Co., Ltd.) were performed in the same manner as in Example 1. The operation yielded 158 g (yield 79%) of 2,5-diethyl adipate as white crystals. Example 3: Synthesis of 2, 5-diethyl adipate except that the starting material was changed to 168.0 g (l. Omol) 2, 5-diethyl-3,4-dihydro-2H-Zhaonan-2-curaldehyde, 99.0g (3.0mol) Hydroxide (Kanto Chemical Co., Ltd.) and 200g of flowing paraffin 60S (central Chemical Co., Ltd.) The same operation as in Example 1 was performed to obtain 131 g of 2,5-diethyl adipate (yield 65%) as white crystals. Reference Example 1: 2,5-diethyl- 3, 4-dihydro-2 Synthesis of H-Gran-2-Carboxaldehyde_ Put the stirrer into a 100ml pressure cooker, add 50g of 2-ethylacryl (made by Aldrich, purity 85%), and react at 150 ~ 160 ° C. 8 Hours, secondly, the reaction solution was distilled off under reduced pressure, and a fraction of 82 to 841/50 Pa was obtained as 2,5-diethyl-3,4-dihydro-2H-gran-2 · carboxaldehyde 36.8 g (yield 87 %). Reference Example 2: Synthesis of 2, 5-diethyltetrahydrogran-2-methanol Put the stirring tablet into a 100 ml pressure cooker and add 10.0 g of 2,5-diethyl- 3,4-dihydro-2H-gran-2-carboxaldehyde and 0.3 g of sponge nickel catalyst (say -12-200418753 N- 1 1 3 manufactured by Hwa Chemical Co., Ltd.) under a hydrogen pressure of 2. 〇 MP A, reaction at 150 ° C for 6 hours. After the reaction, the sponge nickel catalyst was filtered off from the reaction solution, and the obtained filtrate was delivered to the sand tube column for chromatographic analysis. [Solvent: n _ 己 院 / ethyl acetate = 9/1 (capacity ratio)] 'to obtain 9.8 g of 2,5-diethyltetrahydrogran-2-methanol (yield 98%). Reference Example 3: 2, 5-diethyl-3, Synthesis of 4-dihydro-2H-gran-2-methanol Put the stirrer into a pressure cooker with an internal volume of 100m1 and add 2,5-diethyl -3,4-dihydro-2H-gran-2-carboxaldehyde and 0.5g of Cu-Cr catalyst (made by} ^ 1 ^} ^%, 0202?), Hydrogen pressure 2. (^? 3 , At 130. (: Reaction for 50 hours, after the reaction is completed, the Cu-Cr catalyst is filtered off from the reaction solution, and the obtained filtrate is submitted to silica gel column chromatography [solvent: η-hexane / ethyl acetate = 9/1 ( (Capacity ratio)] to obtain 9.6 g of 2,5-diethyl-3,4 · dihydro-2--gran-2-methanol (yield 95%). Effect of the Invention According to the present invention, it is provided in poly The amine modifiers, polyester modifiers, cosmetic bases, raw materials of polyesters or polyamines are useful in industrially suitable production methods of adipic acid.