201249536 六、發明說明： 【發明戶厅屬之技術領域3 發明領域 本發明係關於一種用以製造己二酸及其二酯的羰基化 方法及其用途。本發明亦關於以己二酸為主的聚合物之製 造。 【先前技術3 發明背景 己二酸（1,6-己院二酸)係一種重要的前驅物，尤其是用 於聚醯胺（諸如耐綸6,6或史丹尼爾（Stanyl)TM)之製造。再 者，己二酸之酯類可使用在塑化劑、潤滑劑、溶劑中及在 多種聚胺基甲酸酯樹脂中。己二酸的其它用途有作為食物 酸化劑、應用在黏著劑、殺蟲劑、鞣製及染色中。 製造己二酸的最重要方法係以油為主及從笨開始。在 此方法中，將苯氫化成環己烷。然後，使用hno3作為氧化 劑，將環己烷氧化成己二酸。此方法的缺點為其係以化石 衍生出的油為主。此方法之另一個缺點係差的選擇性，其 導致二酸混合物形成’此引起純化問題。第三缺點為在氧 化步驟期間會放出NOx，其將被排放至空氣，此高度不想 要，因為其係一種溫室氣體；或其可被催化破壞，此係一 種昂貴的方法。已經發展出以丁二烯為主的新己二酸製造 方法。在這些方法之一中，將丁二烯轉換成3-戊烯酸甲酯。 下一個步驟為將3-戊烯酸甲酯異構化成4-戊稀酸甲酯，其可 轉換成己二酸二曱酯。但是，由於沸點的小差異，藉由蒸 4 201249536 餾分離4-戊烯酸酯與3-戊烯酸酯有問題。有時以單一步驟進 行該異構化及曱氧基羰基化。最後，將己二酸二甲醋水解 成己二酸。该以丁一浠為基底的方法之缺點為丁二烯的成 本南。苐·一·缺點為丁·一稀之甲氧基幾基化速率低。因為此， 需要高濃度的鈀觸媒，此導致觸媒快速的去活化。 在WO 2001068583中描述出於羰基化方法中使用式⑴ 之雙牙二膦來羰基化3-戊烯酸曱酯以製備己二酸的二醋， 其包括讓下列物質反應： (a) —包含3-戊烯酸曱酯的組成物； (b) — Pd來源； (c) 一式I的雙牙二膦， RVP-RS-R-R'PW (I) 其中p代表磷原子；R1、R2、R5及R6可各自獨立地代表相同 或不同之選擇性經取代包含三級碳原子的有機基團，其中 透過該三級碳原子將該基團連結至磷原子；R3及R4各自獨 立地代表選擇性經取代的低級伸烷基；及R代表選擇性經取 代的芳香基團； (d) —衍生自具有pKa<3的酸之陰離子來源； (e) 一氧化碳；及 (f) 一含〇H基團的化合物。 WO 2001068583未言明使用式（I)之配位子作為用於2_ 戊烯酸曱酯之轉換的觸媒之部分。 如上所述之包含式(I)之雙牙二膦的羰基化方法已從吉 米内次-羅德里格斯(jin^nez-Rodrigues)等人(Inorg. Chem. 201249536201249536 VI. Description of the Invention: [Technical Field of Invention of the Family Hall 3] Field of the Invention The present invention relates to a carbonylation process for producing adipic acid and its diester and use thereof. The invention also relates to the manufacture of polymers based on adipic acid. [Prior Art 3 Background] Adipic acid (1,6-hexanic acid) is an important precursor, especially for the manufacture of polyamines such as nylon 6,6 or StanylTM. . Further, esters of adipic acid can be used in plasticizers, lubricants, solvents, and in various polyurethane resins. Other uses of adipic acid are as food acidulants, in adhesives, insecticides, tanning and dyeing. The most important method of making adipic acid is based on oil and starting from stupidity. In this method, benzene is hydrogenated to cyclohexane. Then, cyclohexane was oxidized to adipic acid using hno3 as an oxidizing agent. The disadvantage of this method is that it is dominated by fossil-derived oils. Another disadvantage of this method is the poor selectivity which results in the formation of a diacid mixture. This causes purification problems. A third disadvantage is that NOx will evolve during the oxidation step, which will be vented to the air, which is undesirable because it is a greenhouse gas; or it can be catalytically destroyed, which is an expensive process. A new method for the manufacture of butadiene has been developed. In one of these methods, butadiene is converted to methyl 3-pentenoate. The next step is the isomerization of methyl 3-pentenoate to methyl 4-pentamate, which can be converted to dinonyl adipate. However, due to the small difference in boiling point, separation of 4-pentenoate with 3-pentenoate by distillation 4 201249536 is problematic. This isomerization and oxiranyl carbonylation are sometimes carried out in a single step. Finally, the dimethyl acetonate is hydrolyzed to adipic acid. The disadvantage of this method based on Ding Yi is that the cost of butadiene is south.苐··· The disadvantage is that the rate of methoxy grouping of D. Because of this, a high concentration of palladium catalyst is required, which leads to rapid deactivation of the catalyst. The use of a bidentate diphosphine of formula (1) to carbonylate 3-pentenoate in a carbonylation process to produce adipic acid diacetate comprising reacting the following materials is described in WO 2001068583: (a) - Inclusion a composition of decyl pentenoate; (b) - a source of Pd; (c) a didentate diphosphine of formula I, RVP-RS-R-R'PW (I) wherein p represents a phosphorus atom; R1, R2 And R.sup.5 and R.sup.6 and R.sup.6 are each independently represented by the same or different substituents, and the organic group containing a tertiary carbon atom is substituted, wherein the group is bonded to the phosphorus atom through the tertiary carbon atom; R3 and R4 each independently represent a selectively substituted lower alkylene group; and R represents a selectively substituted aromatic group; (d) - an anion source derived from an acid having pKa <3; (e) carbon monoxide; and (f) a ruthenium containing A compound of the H group. WO 2001068583 does not teach the use of a ligand of formula (I) as part of a catalyst for the conversion of decyl 2-pentenoate. The carbonylation process of the bidentate diphosphine comprising formula (I) as described above has been carried out from jin^nez-Rodrigues et al. (Inorg. Chem. 201249536).
Comm. (2005)，vol.8，ρ·878)知曉，其描述出將該二膦使用 在3-戊烯酸甲酯之鈀催化的羰基化中以形成己二酸二甲 酯。他們亦描述出自由態2-戊烯酸之甲氧基羰基化，此造 成己二酸二曱酯形成。但是，吉米内次-羅德里格斯等人未 言明2 -戊烯酸甲酯在該羰基化反應中的用途。 在WO/0248094中描述出一種方法，其中使用式(I)之雙 牙二膦將甲基-3-戊烯酸轉換成己二酸二曱基酯。 在WO 2009010782中描述出可將根據式(I)的雙牙二膦 使用於戊烯酸烷酯（諸如3-戊烯酸曱酯）及戊烯酸類（諸如2-及3-戊烯酸）之羰基化。但是，WO 2009010782未言明2-戊 烯酸甲酯之轉換。 在WO 2006125801中描述出將式(I)之雙牙二膦使用於 2-、3-及4-戊烯酸的羰基化，但非戊烯酸甲酯。 高度想要從可再生資源製造出諸如耐綸-6,6之聚合 物。此方法減低其製造時所放出的C〇2總量，因此幫助緩和 對抗全球暖化。此外，其幫助減慢化石資源之消耗。可從 農業廢料、或來自紙工業的廢棄物、或城市廢棄物製造γ-戊酮酸，因此其構成c-5碎片的可再生來源。已經描述出γ-戍酮酸之氫化及其以高產率產生戊内g旨。一些現存的專利 描述出戊内酯與甲醇於液相或於氣相中之反應，而釋放出 2-戊烯酸曱酯、3_戊烯酸甲酯與4·戊烯酸甲酯之混合物。如 上所述，已報導3-戊烯酸甲酯及4-戊烯酸曱酯轉換成己二酸 二曱酯。但是，2-戊烯酸甲酯存在於從戊内酯之轉換所獲 得的這些混合物中將構成嚴重的問題。在此化合物中’該 6 201249536 雙鍵係在α，β-位置（脉刍-position)及其與酯基團共耗而造 成此鍵的反應性，其總體與在3-或4-戊歸酸甲@旨中的雙鍵不 同。熟練技藝之人士熟知親核基可在稱為1,4-加成的反應中 非常容易地加入至此型式的雙鍵。膦配位子]，4_加成至此烯 烴導致形成穩定的鱗鹽。此係一種已充分文件化的反應， 其尤其已經描述在下列中：C.金柏特（Gimbert) , A.弗利貝 拉(Vallribera)，J.A.葛雷帝曰（Gladysz)，M.裘瑞雪(jurisch)， Leiiens 51(2010)4662-4665 ;及 Μ.荷南戴兹 (Hernandez)及 Ρ.蔻克（Kalck)，Journal of Molecular Catalysis A: Chemical 116(1997)131-146。亦已知此反應係由酸催 化。此方法消耗來自溶液的配位子及因為該觸媒（其係一種 在鈀與磷配位子間之錯合物）僅於過量配位子存在下安 定’此方法導致從觸媒剝除配位子而遺留未配位的金屬。 由熟練技藝之人士熟知的是，在le的情況中，此導致纪黑 形成或更差、鈀電鍍在反應器壁上。在二者情況中，該反 應會停止或變成極慢。該觸媒於2-戊稀酸曱酯存在下之第 二種可能的去活化機制係形成高度穩定的鈀烷基錯合物。 該鈀烷基錯合物之形成為在戊烯酸酯的異構化曱氧基幾基 化中之必需步驟。正常來說，這些鈀烷基錯合物不穩定， 且一旦該端鈀錯合物已經形成’將在異構化中朝向想要的 4-戊烯酸酯快速反應或插入CO。但是，在以2-戊稀酸甲|旨 為主之纪烧基錯合物形成的情況中，可形成安定的5_環結 構’其中該醋基團的幾基配位至纪。此反應型式從下列已 知.J.M.布朗（Brown)及K.K.海依(Hii)，Angew. CTiem. Jni，·五d 201249536 心客/·，1996，35，657-659。因此，此穩定物種之形成將妨 礙所需要的異構化反應。布朗及海依已顯示出需要鹼性條 件來防止此物種形成。不幸的是’戊烯酸酯之鈀催化的幾 基化需要酸性條件。第三問題為在戊烯酸曱酯的全部不同 異構物中’ 2-戊烯酸甲酯最穩定，因為該雙鍵與酯基團共 軛。因此，將非常難以將2-戊烯酸酯異構化成4-戊烯酸酯， 因為後者的能量較高。 戊烯酸甲酯異構物之沸點非常接近，使得非常難以使 用蒸餾從包含3-及/或4-戊烯酸甲酯的混合物中分離出2-戊 稀酸曱酷。 因此，不出人意外的是，尚未描述出2-戊烯酸甲酯或 2-、3-及4-戊烯酸烷酯之混合物的烷氧基羰基化。結果，熟 練的人士將對在羰基化方法中使用曱基-2-戊烯酸來產生己 二酸二酯保持距離。 在WO 02/46143中描述出正戊烯酸衍生物(諸如戊烯酸 甲酯）之羰基化。其描述出該正戊烯酸衍生物可係全部異構 物，諸如2、3及4異構物。雖然WO 02/46143指出該戊烯酸 曱酯可為不同異構物的混合物之事實，WO 02/46143告知該 混合物以包含至少80%的3-戊烯酸甲酯為較佳。但是，其未 揭示出2-戊烯酸曱酯在此混合物中的實際量。再者，在WO 02/46143之實施例中，在該羰基化反應中僅有使用3 -戊烯腈 及3-戊烯酸甲酯。 本發明家已驚人地實現可使用包含2-戊烯酸烷酯的組 成物有效率地製造己二酸烷基二酯。本發明的目標係增加 8 201249536 轉換速度。 t發明内容】 發明概要 在第一觀點中，本發明係關於一種用以製備式I之化 合物的羰基化方法， XOOC-(CH2)4-COOY (I) 其中X及Y可各自獨立地代表Η或烷基，該羰基化方法包括 讓下列物質： (a) —包含至少一種戊烯酸曱酯異構物的組成物； (b) — Pd來源； (c) 一式II的雙牙二膦， r^^.r^r.r^PrSr6 (II) 其中P代表磷原子；R1、R2、R5及R6可各自獨立地代表相 同或不同之選擇性經取代包含三級碳原子的有機基團，其 中透過該三級碳原子將該基團連結至磷原子；R3及R4各自 獨立地代表選擇性經取代的低級伸烷基；及R代表選擇性 經取代的芳香基團； (d) —衍生自具有pKa<3的酸之陰離子來源； (e) —氧化碳；及 (f) 一含OH基圈的化合物， 在產生(I)之條件下反應，其特徵為該最少一種戊烯酸甲酯 異構物包含2-戊烯酸曱酯。 以R3及/或R4所代表的低級伸烷基係未經取代為較 佳。R3及R4可各自獨立地代表-CH2-或-C2H4-。在較佳的具 201249536 體實例中，R、R2、R5及R6係三級丁基；R3及R4係亞甲基； 及R係鄰-伸苯基。 該低級烷基以具有4C原子或較少為較佳，以3C原子 或較少為更佳，甚至更佳為2C原子或較少，最佳為該低級 烷基係甲基。 在一個具體實例中，該式II之烷酸酯係己二酸單酯。 在另一個高度較佳的具體實例中，該式II之烷酸酯係 己二酸二甲基醋。 該2-戊烯酸甲酯可係順-或反-2-戊烯酸曱酯或其混合 物。 本發明家已發現本發明的第一觀點之方法可有利地 具有高轉換速率，及其可使用而不需要從亦包含3-及/或4-戊烯酸曱酯的混合物中分離出2 -戊烯酸曱酯來異構化2 -戊 烯酸曱酯。該方法對從可再生來源（諸如植物廢棄物、污 水廢棄物等等之物）取代使用化石來源來製造己二酸二甲 基醋有益。 本發明之方法選擇性於額外的溶劑存在下進行。實務 上，己二酸的二酯或在觸媒的再循環期間發展出之重物質 (heavier)可作用為溶劑。該額外的溶劑以非質子溶劑為較 佳。合適的溶劑包括酮類，諸如例如曱基丁基酮；醚類， 諸如例如茴香醚（甲基苯基醚）、2,5,8-三氧壬烷（二甘醇二 甲謎）、二乙基鍵、四氫咬喃、2-曱基-四氫0夫喃、二苯基 醚、二異丙基醚及二乙二醇的二甲基醚；酯類，諸如例如 醋酸乙酯、醋酸曱酯、己二酸二曱酯及丁内酯；醯胺類， 10 201249536 諸如例如二曱基乙醯胺及N-甲基吡咯烷酮；及亞砜類及砜 類’諸如例如二甲基㈣ '二異丙級、環丁硬（四氮喧 吩-2,2-二氧化物）' 2-曱基環丁碾及2_曱基_4乙基環丁砜。 非常合適的是在298.15反及丨巴下具有介電常數值低於％ 之非質子溶劑’在範圍3至8更佳。若該含羥基的化合物係 烷醇時，進一步較佳的非質子溶劑為式丨之化合物、一氧 化碳與烷醇的酯羰基化產物。 在本發明之方法中，合適的Pd來源包括其鹽類，諸如 例如鈀與il化物酸、硝酸、硫酸或磺酸之鹽；鈀錯合物， 例如含有一氧化碳、二烯（諸如二亞节基丙酮(dba)或乙醯 丙_酸鹽）之鈀奈米粒子或與固體載體材料(諸如碳 '二氧 化矽或咸子父換器）結合的把。較佳的是，使用把與羧酸 之鹽，合適的是，具有最高12個碳原子的羧酸(諸如醋酸、 丙釀、丁酸或2-乙基-己酸)之鹽、或經取代的羧酸(諸如三 氣醋酸及三氟醋酸)之鹽。非常合適的來源為醋酸鈀(ιι)。 在較佳的具體實例中，Pd來源係選自於由下列所組成 之群：鹵化纪、叛酸把及Pd2(dba)3。 式1之雙牙膦對鈀的莫耳比率以1_2〇為較佳，更佳為 1-1〇，甚至更佳為2-6。 合適的反應溫度在範圍20-16CTC内，更佳的範圍係 5〇-12〇t。 在本發明之方法中的壓力在5至100巴間較佳，在丨〇至 50巴間更佳。 若該含OH基團化合物係院醇時，獲得酯類。更佳的 11 201249536 是，該含OH基團化合物係醇，最佳係曱醇。 在具體實例中，該含OH基團化合物係水。 遍及此專利說明書，“己二酸二甲基酯’’及“己二酸二 甲酯”經了解具有相同意義。 衍生自具有pKa低於3.0(在18°C下，於水溶液中測量） 的酸之陰離子來源為非配位用陰離子較佳。藉此意謂著在 鈀與該陰離子間發生些微或無共價交互作用。 合適的陰離子實施例包括磷酸、硫酸、磺酸及經鹵化 的羧酸(諸如三氟醋酸)之陰離子。 磺酸特別佳，諸如例如三氟曱烷磺酸、對曱苯磺酸及 2,4,6-三曱基苯磺酸、2-羥基丙烷-2-磺酸、三級丁基磺酸、 曱基磺酸。該酸亦可為包含磺酸基團的離子交換樹脂。 甚至更佳的有曱基磺酸、三級丁基磺酸及2,4,6-三甲 基苯績酸。 陰離子來源與鈀之莫耳比率以在1 : 1至100 : 1間為較 佳及以在1 : 1至10 : 1間為更佳。 在本上下文中，所提供的溶劑之介電常數以其正常意 義使用，其表示含有該物質作為介電質的電容器之容量對 具有真空作為介電質的相同電容器之容量的比率。常見的 有機液體之介電常數值可在一般參考書中找到，諸如化學 及物理手冊（Handbook of Chemistry and Physics)，第 76 版，由大衛(David)R.萊德（Lide)等人編輯，及由CRC出版 社在1995年出版，及通常引述的溫度約20或25°C(即，約 293.15或298.15 K)及大氣壓（即，約1巴），或可使用所引述 12 201249536 的轉換因子容易地轉換成該溫度及壓力。若特別的化合物 無可獲得的文獻資料時，該介電常數可使用已建立的物理 化學方法容易地測量。 例如，茴香醚的介電常數為4.3(在294.2K)，二乙爲鱗 為4.3(在293.2K) ’環丁砜為43.4(在303.2K)，丙酸曱g旨為 5.0(在293.2K)，二苯基醚為3.7(在283·2Κ)，己二酸二甲嗎 為6.8(在293.2Κ)，四氫呋喃為7.5(在295.2Κ)，壬酸甲g旨為 3.9(在293.2K)。 2-戊烯酸甲酯在該組成物中之量較佳為3重量％，更 佳為在5-85重量％、6-80重量％間，甚至更佳在7_7〇重量 %、8-60重量％間，甚至更佳在9-50重量％、10-40重量％ 間，甚至更佳在11-30重量％、12-20重量％間。 在較佳的具體實例中，該至少一種戊烯酸曱酯異構物 為一包含順-及/或反-2-戊烯酸甲酯及順_及/或反_3_戊稀酸 甲酯及/或甲基-4-戊烯酸醋的混合物。該混合物可例如包 含2-戊烯酸甲酯與3-戊烯酸甲酯、2_戊烯酸甲酯與4_戊烯 酸甲酯、或2-戊烯酸曱酯、3-戊烯酸曱酯與4_戊烯酸甲醋。 該包含至少一種戊烯酸曱酯異構物的組成物町包含 其它組分，諸如自由態戊烯酸類(2-戊烯酸、3-戊烯酸及/ 或4-戊稀酸）。該戊稀酸類的總量較佳為少於1〇重量％。該 包含至少一種戊烯酸甲酯異構物的組成物亦可包含戊内 酉旨。 該包含至少一種戊烯醆曱酯異構物的組成物亦巧包 含水’以在0.1至3重量％間為較佳。小量的水可優良，因 13 201249536 為其可加速該轉換速率(T0F，小時-1)0較佳的是’在該包 含至少一種戊烯酸曱酯異構物的組成物中之水量在〇13至 3重量％間，以在0.19至3%間、在〇19至2 55重量％間為更 佳，在0.24至2.55重量％間甚至更佳，在〇51至2 55重量％ 間甚至更佳。 一氧化碳分壓在範圍1-65巴内為較佳。在根據本發明 的方法中，一氧化碳可以其純形式或以惰性氣體（諸如 氮、二氧化碳)或貴氣體(諸如氬)稀釋使用。亦可存在少量 氫。通常來說，不想要存在多於5%的氫，因為此可造成 戊烯酸酯類之氫甲醯化或甚至氫化。 在根據本發明的第一觀點之方法中所使用的鈀量係 使用由熟練技藝之人士已知的疊代方法徹底最佳化的結 果。然而，咼Ιε濃度導致非常快速的反應，它們亦可導致 鈀黑形成。此後者去活化過程藉由配位子及戊烯酸酯類之 存在而改善。鈀黑形成亦藉由高溫加速。通常來說，每莫 耳戊烯酸酯類1〇·7至10·1克原子的範圍將係此最佳化之起 始點。更可能的是，該鈀量將在每莫耳戊烯酸酯10-5至1〇·2 克原子的範圍内。 在第二觀點中，本發明提供一種製造己二酸二曱基酯 的方法，該方法包括： (a) 藉由於酸性或鹼性觸媒存在下，在氣相或在液相 中，以曱醇處理將戊内酯轉換成戊烯酸甲酯類之混合物， 其包含25重量％的2-戊烯酸甲酿；及 (b) 使用根據本發明的第一觀點之羰基化方法，將在步 201249536 驟(a)中所製造的戊烯酸曱酯混合物轉換成己二酸二曱基 酯’其中該含OH基團的化合物係甲醇。 本發明家已驚人地發現本發明的第二觀點之方法可 有利地進行而在步驟(a)後及在步驟(b)前沒有額外的步驟 (諸如純化或分離步驟），來移除或減少曱基-2-戊烯酸的 量〇 在步驟(a)中將戊内酯轉換成戊烯酸甲酯類之混合物 可在液相或在氣相中完成，以釋放出2-戊烯酸曱酯、3-戊 烯酸甲酯與4-戊烯酸甲酯之混合物。此方法描述在WO 2005058793、WO 2004007421 及US 4740613 中。 在具體實例中，戊内酯係藉由氫化反應將r-戊酮酸 轉換成戊内酯而製備。此方法描述在L.E.門惹（Manzer)， Appl. Catal. A > 2004 > 272 > 249-256 ； J.P. i # (Lange) > J.Z. 維斯林（Vestering)及 R.J.哈恩（Haan)，CTiem. Commim.， 2007，3488-3490 ; R_A.鮑内（Bourne)，J.G.史狄芬斯 (Stevens)，J.奇（Ke)及 M.波里阿柯夫（Poliakoff)，CTiem. ’ 2007，4632-4634 ; H.S.布羅得班特（Broadbent)， G.C.坎貝爾（Campbell)，W.J.巴托利（Bartley)及 J.H.強森 (Johnson)，·/. C7iem_，1959，24，1847-1854 ; R_V.克 麗斯啼安(Christian.)，H.D.布朗及R.M.希松(Hixon)，《/. Am. C/iem. Soc· ’ 1947，69，1961-1963 ; L.P.奇瑞戴斯(Kyrides) 及 J.K.克瑞弗（Craver)，美國專利，2368366，1945 ; H.A. 薛特（Schuette)及 R.W.湯瑪斯（丁11〇11138)，1/.焱/72.^71撕· Soc.，1930，52，3010-3012 中。 15 201249536 在另一個具體實例中，γ-戊酮酸係藉由酸催化的反應 將C6碳水化合物轉換成丫-戊_酸而製備。此方法例如描述 在L_J·卡爾森(Carlson)，美國專利，3065263，1962 ; Β.吉 里蘇塔（Girisuta)，L.P.B.M·珍森（Janssen)及 H.J.布瑞斯 (Heeres) » Chem. Eng. Res. Des. » 2006 > 84 > 339-349 ； B.F.M. 酷斯特（Kuster)及 H.S.凡德巴恩（Vanderbaan)， ，1977，54，165-176 ; S.W.菲次派翠克（Fitzpatrick)， WO8910362，1989，由拜爾芬内有限公司（Biofine Incorporated) ; S.W.菲次派翠克，w〇 96406091996，由拜 爾芬内有限公司中。該C6碳水化合物的實施例有葡萄糖、 果糖、甘露糖及半乳糖。該C6碳水化合物的較佳原料有包 含以碳水化合物為基底的聚合物部分或全部由C6糖類組 成之木質纖維素材料，諸如木質纖維、纖維素、澱粉及半 纖維素。該C6碳水化合物可包含其它組分，諸如植物廢棄 物、污水等等。 根據本發明之第二觀點的製造己二酸之方法有利地 允許使用可再生來源(諸如植物廢棄物、來自紙製造之廢 棄物、污水廢棄物等等之物)取代使用化石來源。 在較佳的具體實例中，根據本發明的第二觀點之方法 包括分離己一酸二甲酯，例如藉由蒸館。可將包含未轉換 的戊烯酸甲酯及/或觸媒之蒸餾殘餘物(及其仍然可包含某 些己二酸二曱酯）再循環回反應器中。 在具體實例中，DMA在水解反應十水解成己二酸。 DMA水解成己二酸由熟知技藝之人士所熟知β該水解以藉 16 201249536 由酸性觸媒催化為較佳。 在另一個具體實例中，己二酸酯（adipate)藉由以氨處 理轉換成己二酸錄。 在另一個具體實例中，己二酸銨在脫水反應中轉換成 己二腈。 在另一個具體實例中，己二腈在還原反應中轉換成己 二胺。己二酸酯轉換成己二酸銨、從己二酸銨至己二腈及 從己一腈至己二胺由熟知該技藝之人士已知，及例如由弗 内里爾斯（Fernelius)等人所描述（Journal of Chemical Education，1979，vol.56，p.654-656)。Comm. (2005), vol. 8, ρ 878, is known to describe the use of the diphosphine in palladium catalyzed carbonylation of methyl 3-pentenoate to form dimethyl adipate. They also describe the methoxycarbonylation of free 2-pentenoic acid, which results in the formation of dinonyl adipate. However, Jimi Nei-Rodriguez et al. did not state the use of methyl 2-pentenoate in the carbonylation reaction. A process is described in WO/0248094 in which methyl-3-pentenoic acid is converted to dinonyl adipate using the bidentate diphosphine of formula (I). It is described in WO 2009010782 that a bidentate diphosphine according to formula (I) can be used for alkyl pentenoates (such as decyl pentenoate) and pentenoic acids (such as 2- and 3-pentenoic acid). Carbonylation. However, WO 2009010782 does not teach the conversion of methyl 2-pentenoate. The use of the bidentate diphosphine of formula (I) for the carbonylation of 2-, 3- and 4-pentenoic acid, but not methyl pentenoate, is described in WO 2006125801. It is highly desirable to manufacture polymers such as nylon-6,6 from renewable resources. This method reduces the total amount of C〇2 released during its manufacture, thus helping to alleviate global warming. In addition, it helps to slow down the consumption of fossil resources. Γ-pentanone acid can be produced from agricultural waste, or waste from the paper industry, or municipal waste, and thus constitutes a renewable source of c-5 chips. Hydrogenation of gamma-indolone acid and its production in a high yield have been described. Some existing patents describe the reaction of valerolactone with methanol in the liquid phase or in the gas phase to release a mixture of decyl 2-pentenoate, methyl 3-pentenoate and methyl 4-pentenoate. . As described above, methyl 3-pentenoate and decyl 4-pentenoate have been reported to be converted to dinonyl adipate. However, the presence of methyl 2-pentenoate in these mixtures obtained from the conversion of valerolactone poses a serious problem. In this compound, the 6 201249536 double bond is responsible for the bond at the α, β-position and its co-consumption with the ester group, and its overall relationship with 3- or 4-week The double bond of the acid A is different. It is well known to those skilled in the art that nucleophilic groups can be readily added to this type of double bond in a reaction known as 1,4-addition. The phosphine ligand], 4_ addition to this olefin leads to the formation of stable scale salts. This is a fully documented reaction, which has been described in particular in the following: C. Gimbert, A. Vallribera, JA Gladysz, M. (Jurisch), Leiiens 51 (2010) 4662-4665; and Μ. Hernandez and Kalck, Journal of Molecular Catalysis A: Chemical 116 (1997) 131-146. This reaction is also known to be acid catalyzed. This method consumes the ligand from the solution and because the catalyst (which is a complex between the palladium and the phosphorus ligand) settles only in the presence of excess ligand. This method results in stripping from the catalyst. The seat left the uncoordinated metal. It is well known to those skilled in the art that in the case of le, this results in darker formation or worse, palladium plating on the reactor wall. In both cases, the reaction will stop or become extremely slow. The second possible deactivation mechanism of the catalyst in the presence of decyl 2-pentanoate forms a highly stable palladium alkyl complex. The formation of the palladium alkyl complex is an essential step in the isomerization of the pentenoic acid ester. Normally, these palladium alkyl complexes are unstable, and once the palladium complex is formed, 'will react rapidly or insert CO into the desired 4-pentenoate in isomerization. However, in the case of the formation of a complex of a complex of 2-pentaic acid, a stable 5-ring structure can be formed in which the groups of the acetate group are coordinated to the present. This reaction pattern is known from the following. J. M. Brown and K. K. Hayi, Angew. CTiem. Jni, · 5d 201249536, et al., 1996, 35, 657-659. Therefore, the formation of this stable species will hinder the isomerization reaction required. Brown and Haiyi have shown that alkaline conditions are needed to prevent the formation of this species. Unfortunately, the palladium catalyzed localization of 'pentenoate esters requires acidic conditions. The third problem is that methyl 2-pentenoate is most stable in all the different isomers of decenoate, since the double bond is conjugated to the ester group. Therefore, it will be very difficult to isomerize 2-pentenoate to 4-pentenoate because the latter has a higher energy. The boiling point of the methyl pentenoate isomers is very close, making it very difficult to separate 2-pentane acid from a mixture comprising methyl 3- and/or 4-pentenoate using distillation. Therefore, it is not surprising that the alkoxycarbonylation of a mixture of methyl 2-pentenoate or an alkyl 2-, 3- and 4-pentenoate has not been described. As a result, a skilled person will maintain the distance by using mercapto-2-pentenoic acid in the carbonylation process to produce adipic acid diester. The carbonylation of n-pentenoic acid derivatives, such as methyl pentenoate, is described in WO 02/46143. It is described that the n-pentenoic acid derivative may be all isomers such as the 2, 3 and 4 isomers. While WO 02/46143 teaches the fact that the decenoate may be a mixture of different isomers, WO 02/46143 teaches that the mixture preferably comprises at least 80% methyl 3-pentenoate. However, it does not reveal the actual amount of decyl 2-pentenoate in this mixture. Further, in the examples of WO 02/46143, only 3-pentenenitrile and methyl 3-pentenoate are used in the carbonylation reaction. The present inventors have surprisingly realized that an adipic acid alkyl diester can be efficiently produced using a composition comprising an alkyl 2-pentenoate. The goal of the present invention is to increase the conversion speed of 8 201249536. SUMMARY OF THE INVENTION In a first aspect, the invention relates to a process for the carbonylation of a compound of formula I, XOOC-(CH2)4-COOY (I) wherein X and Y each independently represent hydrazine Or an alkyl group, the carbonylation process comprising the following: (a) - a composition comprising at least one isomer of pentenoate pentate; (b) - a source of Pd; (c) a bidentate diphosphine of formula II, R^^.r^rr^PrSr6 (II) wherein P represents a phosphorus atom; R1, R2, R5 and R6 each independently represent the same or different selective substitution of an organic group comprising a tertiary carbon atom, wherein The tertiary carbon atom binds the group to the phosphorus atom; R3 and R4 each independently represent a selectively substituted lower alkyl group; and R represents a selectively substituted aromatic group; (d) - derived from An anion source of acid of pKa<3; (e) - carbon oxide; and (f) a compound containing an OH group ring, reacted under the conditions of (I), characterized by a minimum of one methyl pentenoate The construct comprises decyl 2-pentenoate. It is preferred that the lower alkylene group represented by R3 and/or R4 is unsubstituted. R3 and R4 may each independently represent -CH2- or -C2H4-. In a preferred embodiment of 201249536, R, R2, R5 and R6 are tertiary butyl; R3 and R4 are methylene; and R is o-phenyl. The lower alkyl group is preferably 4C atoms or less, more preferably 3C atoms or less, even more preferably 2C atoms or less, most preferably the lower alkyl group methyl group. In one embodiment, the alkanoate of formula II is adipic acid monoester. In another highly preferred embodiment, the alkanoate of formula II is adipic acid dimethyl vinegar. The methyl 2-pentenoate may be cis- or trans-2-pentenoate or a mixture thereof. The inventors have found that the process of the first aspect of the invention advantageously has a high rate of conversion and that it can be used without the need to separate 2- from a mixture which also comprises 3- and/or 4-pentenoate. Ethyl pentenoate to isomerize 2-non-2-pentenoate. This method is beneficial for the production of adipic acid dimethyl vinegar by replacing the use of fossil sources from renewable sources such as plant waste, sewage waste, and the like. The process of the invention is optionally carried out in the presence of an additional solvent. In practice, the diester of adipic acid or the heavier developed during the recycling of the catalyst can act as a solvent. The additional solvent is preferably an aprotic solvent. Suitable solvents include ketones such as, for example, mercaptobutyl ketone; ethers such as, for example, anisole (methylphenyl ether), 2,5,8-trioxane (diethylene glycol dimethyl mystery), Ethyl bond, tetrahydroanion, 2-mercapto-tetrahydrofuran, diphenyl ether, diisopropyl ether and dimethyl ether of diethylene glycol; esters such as, for example, ethyl acetate, Ethyl acetate, dinonyl adipate and butyrolactone; decylamines, 10 201249536 such as, for example, dimercaptoacetamide and N-methylpyrrolidone; and sulfoxides and sulfones such as, for example, dimethyl (tetra) 'Diisopropyl, cyclobutyl hard (tetrazine phenanthrene-2,2-dioxide)' 2-mercaptocyclobutane and 2_mercapto-4 ethyl sulfolane. It is very suitable that the aprotic solvent having a dielectric constant value of less than % at 298.15 and 丨 is more preferably in the range of 3 to 8. Further, when the hydroxyl group-containing compound is an alkanol, a further preferred aprotic solvent is a compound of the formula, an ester carbonylation product of carbon monoxide and an alkanol. In the process of the present invention, suitable sources of Pd include salts thereof such as, for example, salts of palladium with il acid, nitric acid, sulfuric acid or sulfonic acid; palladium complexes such as carbon monoxide, diene (such as di-subunits) A palladium nanoparticle of acetone (dba) or acetophenone-acid salt or a combination of a solid carrier material such as carbon's cerium oxide or salty sub-replacer. Preferably, a salt with a carboxylic acid, suitably a salt of a carboxylic acid having up to 12 carbon atoms, such as acetic acid, propylene, butyric acid or 2-ethyl-hexanoic acid, or substituted a salt of a carboxylic acid such as tri-acetic acid and trifluoroacetic acid. A very suitable source is palladium acetate (ιι). In a preferred embodiment, the source of Pd is selected from the group consisting of halogenated, tartarian, and Pd2(dba)3. The molar ratio of the bidentate phosphine of the formula 1 to palladium is preferably 1 Torr, more preferably 1-1 Torr, even more preferably 2-6. Suitable reaction temperatures are in the range of from 20 to 16 CTC, more preferably in the range of from 5 to 12 Torr. The pressure in the process of the invention is preferably between 5 and 100 bar, more preferably between 50 and 100 bar. If the OH group-containing compound is an alcohol, an ester is obtained. More preferably 11, 201249536 is the OH group-containing compound alcohol, the best sterol. In a specific example, the OH group-containing compound is water. Throughout this patent specification, "dimethyl dimethyl adipate" and "dimethyl dimethyl adipate" are understood to have the same meaning. Derived from having a pKa of less than 3.0 (measured in aqueous solution at 18 ° C) The source of the anion of the acid is preferably an anion for non-coordination, whereby it means that there is little or no covalent interaction between the palladium and the anion. Suitable examples of anions include phosphoric acid, sulfuric acid, sulfonic acid and halogenated carboxylic acid. Anion of an acid such as trifluoroacetic acid. Sulfonic acid is particularly preferred, such as, for example, trifluorodecanesulfonic acid, p-toluenesulfonic acid, and 2,4,6-trimercaptobenzenesulfonic acid, 2-hydroxypropane-2- Sulfonic acid, tert-butyl sulfonic acid, mercapto sulfonic acid. The acid may also be an ion exchange resin containing sulfonic acid groups. Even more preferred are mercapto sulfonic acid, tertiary butyl sulfonic acid and 2, 4 , 6-trimethylbenzene acid. The molar ratio of anion source to palladium is preferably between 1:1 and 100:1 and more preferably between 1:1 and 10:1. The dielectric constant of the supplied solvent is used in its normal sense, which means that the capacity of the capacitor containing the substance as the dielectric has true The ratio of the capacity of the same capacitor as the dielectric. The dielectric constant values of common organic liquids can be found in general reference books, such as the Handbook of Chemistry and Physics, 76th edition, by David. (David) edited by R. Led et al., and published by the CRC Press in 1995, and usually quoted at temperatures of about 20 or 25 ° C (ie, about 293.15 or 298.15 K) and atmospheric pressure (ie, about 1 bar), or can be easily converted to the temperature and pressure using the conversion factor of 12 201249536. If there is no available literature for a particular compound, the dielectric constant can be easily measured using established physicochemical methods. For example, anisole has a dielectric constant of 4.3 (at 294.2K), a dimer of 4.3 (at 293.2K), a sulfolane of 43.4 (at 303.2K), and a propionate of g of 5.0 (at 293.2K). Diphenyl ether was 3.7 (at 283. 2 Torr), adipic acid was 6.8 (at 293.2 Κ), tetrahydrofuran was 7.5 (at 295.2 Κ), and citric acid was 3.9 (at 293.2 K). The amount of methyl 2-pentenoate in the composition is preferably 3% by weight, more preferably from 5 to 85% by weight, 6 Between 80% by weight, even more preferably between 7-7 wt%, 8-60 wt%, even more preferably between 9-50 wt%, 10-40 wt%, even more preferably 11-30 wt%, 12 Between -20% by weight. In a preferred embodiment, the at least one isomer of pentenoic acid pentate is one comprising methyl cis- and/or trans-2-pentenoate and cis- and/or anti- Mixture of 3_methyl pentanoate and/or methyl-4-pentenoic acid vinegar. The mixture may, for example, comprise methyl 2-pentenoate and methyl 3-pentenoate, methyl 2-pentenoate and methyl 4-pentenoate, or decyl 2-pentenoate, 3-pentene Acid oxime ester and 4-pentenoic acid methyl vinegar. The composition comprising at least one isomer of pentenoate pentate contains other components such as free pentenoic acids (2-pentenoic acid, 3-pentenoic acid and/or 4-pentamic acid). The total amount of the pentonic acid is preferably less than 1% by weight. The composition comprising at least one methyl pentenoate isomer may also comprise a pentane. The composition comprising at least one of the pentene oxime ester isomers also preferably contains water in an amount of between 0.1 and 3% by weight. A small amount of water can be excellent because 13 201249536 can accelerate the conversion rate (T0F, hour -1). Preferably, the amount of water in the composition comprising at least one isomer of pentenoic acid pentate is Between 13 and 3 wt%, more preferably between 0.19 and 3%, between 19 and 255% by weight, even more preferably between 0.24 and 2.55% by weight, even between 〇51 and 2555% by weight. Better. The partial pressure of carbon monoxide is preferably in the range of from 1 to 65 bar. In the process according to the invention, carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or a noble gas such as argon. A small amount of hydrogen may also be present. In general, it is not desirable to have more than 5% hydrogen, as this can result in hydroformylation or even hydrogenation of the pentenoates. The amount of palladium used in the process according to the first aspect of the invention is the result of thorough optimization using an iterative method known to those skilled in the art. However, the 咼Ιε concentration results in very rapid reactions, which can also lead to the formation of palladium black. The subsequent deactivation process is improved by the presence of ligands and pentenoates. Palladium black formation is also accelerated by high temperatures. In general, the range of 1 〇·7 to 10·1 gram per mole of glutaryl ester will be the starting point for this optimization. More likely, the amount of palladium will be in the range of 10-5 to 1 〇 2 gram per mole of valerate. In a second aspect, the present invention provides a process for producing dinonyl adipate, the process comprising: (a) in the presence of an acidic or basic catalyst, in the gas phase or in the liquid phase, Alcohol treatment converting valerolactone to a mixture of methyl pentenoates comprising 25% by weight of 2-pentenoic acid; and (b) using a carbonylation process according to the first aspect of the invention, Step 201249536 The decyl pentenoate mixture produced in the step (a) is converted into dinonyl adipate, wherein the OH group-containing compound is methanol. The inventors have surprisingly found that the method of the second aspect of the invention can be advantageously carried out without additional steps (such as purification or separation steps) after step (a) and before step (b) to remove or reduce Amount of mercapto-2-pentenoic acid The conversion of valerolactone to methyl pentenoate in step (a) can be carried out in the liquid phase or in the gas phase to release 2-pentenoic acid. A mixture of decyl ester, methyl 3-pentenoate and methyl 4-pentenoate. This method is described in WO 2005058793, WO 2004007421 and US 4740613. In a specific example, valerolactone is prepared by converting r-pentanone acid to valerolactone by a hydrogenation reaction. This method is described in LE Menzan, Appl. Catal. A > 2004 > 272 >249-256; JP i # (Lange) > JZ Wesseling and RJ Haan, CTiem Commim., 2007, 3488-3490; R_A. Bourne, JG Stevens, J. and M. Poliakoff, CTiem. ' 2007, 4362 4634; HS Broadbent, GC Campbell, WJ Bartley and JH Johnson, ·/. C7iem_, 1959, 24, 1847-1854; R_V. Christian., HD Brown and RM Hixon, /. Am. C/iem. Soc· ' 1947, 69,1961-1963 ; LP Cherydes and JK Crawford (Craver), US Patent, 2368366, 1945; HA Schuette and RW Thomas (Ding 11〇11138), 1/.焱/72.^71 tear·Soc., 1930, 52, 3010-3012 in. 15 201249536 In another embodiment, gamma-pentanone acid is prepared by converting an C6 carbohydrate to a quinone-valeric acid by an acid catalyzed reaction. This method is described, for example, in L_J. Carlson, U.S. Patent No. 3,056,263, 1962; Girisuta, LPBM, Janssen, and HJ, Heeres » Chem. Eng. Res Des. » 2006 > 84 >339-349; BFM Kuster and HS Vanderbaan, 1977, 54, 165-176; SW Fitzpatrick, WO8910362, 1989, by Biofine Incorporated; SW Philippe Patrick, w〇96406091996, by Bayerfint GmbH. Examples of such C6 carbohydrates are glucose, fructose, mannose and galactose. Preferred materials for the C6 carbohydrate include lignocellulosic materials comprising, in whole or in part, a C6 saccharide, such as lignocellulosic, cellulose, starch and hemicellulose. The C6 carbohydrate may contain other components such as plant waste, sewage, and the like. The method of producing adipic acid according to the second aspect of the present invention advantageously allows the use of a fossil source instead of a renewable source such as plant waste, waste from paper manufacture, sewage waste, and the like. In a preferred embodiment, the method according to the second aspect of the invention comprises isolating dimethyl hexanoate, for example by steaming. A distillation residue comprising unconverted methyl pentenoate and/or a catalyst (and which may still contain some dinonyl adipate) may be recycled back to the reactor. In a specific example, DMA is hydrolyzed to adipic acid in a hydrolysis reaction. Hydrolysis of DMA to adipic acid is well known to those skilled in the art. The hydrolysis is preferably catalyzed by an acidic catalyst by means of 16 201249536. In another embodiment, the adipate is converted to adipic acid by treatment with ammonia. In another embodiment, ammonium adipate is converted to adiponitrile in a dehydration reaction. In another embodiment, the adiponitrile is converted to hexamethylenediamine in a reduction reaction. The conversion of adipate to ammonium adipate, from ammonium adipate to adiponitrile and from hexonitrile to hexamethylene diamine is known to those skilled in the art and, for example, by Fernelius et al. (Journal of Chemical Education, 1979, vol. 56, p. 654-656).
【實施方式J 下列實施例僅用於闡明目的及不欲解釋為限制本發 明。 實施例 實施例1-3戊烯酸甲酯類之混合物的製備 在大氣壓下，將觸媒（葛雷絲-大衛森(Grace-Davison)/ 大衛凱特(Davicat)SIAL 3501，21.2克）負載進管狀氣相反 應器中，然後加熱至255。(：。以溫度計監視在反應器内的 反應溫度。在引進該進料前，於氮氣流下達成想要的反應 溫度及壓力。使用布魯克斯(Br〇〇ks)質流控制器控制到達 該反應器的氣體流。在到達想要的條件後，製備在皿6〇11 中的γ-戊内酯溶液(1 : 1，以重量計），預先加熱至19〇。〇及 使用ΗΡΙΧΙ進料残填料床f狀反應器 。於周溫下，在 t 出物用於定量分析及藉由GC分析。 17 201249536 LHSV w.r.t.戊内酯係0.49。蒸館來自三次不同運轉的樣 品。來自這三次運轉的主要餾分之組成物列在下列表i 中。在全部混合物中’存在多於5莫耳％的2-戊烯酸曱酯。 表1在從戊内酯與曱醇間之氣相反應所獲得的混合物中 __之戊烯酸甲酯類的皙晋百分比 實 施 例 MeOH m/m % C-M2P m/m % M4P m/m % tr-M3P m/m % C-M3P m/m % tr-M2P m/m % 戊内酯 m/m % 水 m/m % 總共 m/m % 1 1.1 2.2 25.0 44.6 16.3 8.7 1.1 1.1 100 2 0.0 0.8 18.3 48.3 17.5 11.7 0.8 0.8 98 3 0.0 1.6 12.9 48.4 17.7 14.5 1.6 1.6 98 實施例4-戊烯酸曱酯類的甲氧基羰基化 將α，α’-雙(二三級丁基膦基)-鄰-二曱苯(20微莫耳，來 自史春化學公司（Strem Chemicals Inc.)，15，Rue de I’Atome，Z.I.，67800 比奇漢姆(BISCHHEIM)，法國）；5 當量在5毫升曱醇中）溶液加入至Pd前驅物（4微莫耳 Pd(OAc)2)。將甲磺酸(MSA，4微升，40微莫耳，1〇當量） 加入至該觸媒溶液，在此之後，顏色從黃色改變至橙色。 加入基質（2-戊烯酸甲酯、3-戊烯酸甲酯、或2-戊烯酸曱 酯' 3-戊烯酸甲酯與4-戊烯酸甲酯之混合物，如在實施例 1-3中獲得或以1 : 1 : 1比率預製(pre-maid))，及將該混合 物移進英戴弗（Endeavour)(8個安裝有上部攪拌器之小壓 力鋼裝置）的玻璃插管中。以N2沖洗反應器5次，之後以20 巴的CO 10次。將反應器加壓至20巴及加熱至所指示的反 應溫度。在1小時後，將反應容器冷卻至室溫及釋放壓力β 18 201249536 藉由GC分析決定對己二酸二甲酯的轉換及選擇性（表2)。 (M2P=2-戊烯酸曱酯；M3P=3-戊稀酸甲酯； 戊烯酸甲酯；TOF=更新頻率=每莫耳觸媒每小時獲得的產 物莫耳數。藉由在戊内酯與曱醇間之反應，於氣相反應中 獲得M2P、M3P與M4P之混合物，如上所述） 表2戊烯酸曱酯類的曱氧基羰基化 實 施 例 基質 溫度 (°C) TOF (小時丨) 、二甲酯的 選擇性(％、 4 Μ2Ρ 50 105 100' 5 Μ2Ρ 75 289 Γ〇〇 6 Μ2Ρ 100 417 根據本發 日日夕古Ά yl 7 來自實施例1的混合物 75 362 ^ yj /ζτ 的實施例 8 來自實施例2的混合物 75 335 loo' 9 來自實施例3的混合物 75 482 97 10 M2P'M3P'M4P (1:1:1) 75 309 100 11 Μ2Ρ'Μ3Ρ>Μ4Ρ (1:1:1) 100 342 12 Μ3Ρ 50 141 loo 比較例 13 Μ3Ρ 75 281 loo ^ 14 Μ3Ρ 100 332 —. 表2顯示出2-戊烯酸曱酯可在50、75及100°C下以與3_ 戊烯酸甲酯實際上相同的速率及相同的選擇性轉換。此 外，包含2-戊烯酸甲酯、3-戊稀酸甲酯及4-戊烯酸甲自旨的 混合物亦以與3-戊烯酸甲酯相同的速率及選擇性轉換成 己二酸甲酯。此實驗顯示出可使用藉由轉換戊内酯所獲得 的戊烯酸甲酯類之混合物在甲氧基羰基化反應中轉換成 己二酸二甲酯，及在此混合物中存在有2-戊烯酸甲酯而不 具有副作用。 實施例13-19加入水的效應 19 201249536 將α,α’-雙（二三級丁基膦基)-鄰-二甲苯(40微莫耳，5 當量）在4毫升曱醇中的溶液加入至Pd前驅物（8微莫耳 Pd(OAc)2)。將曱磺酸(8微升，80微莫耳，10當量）力口入至 該觸媒溶液，在此之後，可看見顏色從黃色改變至橙色。 加入戊烯酸曱酯（6.4毫莫耳）及水，且將該混合物轉移進入 玻璃英戴弗（Endeavor)插管中。以N2沖洗反應器5次，之後 以20巴的CO 10次。以CO將該反應器加壓至20巴及加熱至 所指示出的反應溫度。在1小時後，將反應容器冷卻至室 溫及釋放壓力。藉由GC分析決定轉換及選擇性。精確的 水量係藉由卡爾費希爾（Karl Fisher)滴定法決定。結果顯 示在表3中。 表3水的效應 實施例 水的重量％ C(%) 對DMA的選 擇性(％) T0F (小時 -丨） 13 0.13 75 95 562 14 0.19 78 96 591 15 0.24 79 97 598 16 0.51 78 94 611 17 1.185 75 96 591 18 1.7 70 91 547 19 2.55 68 91 534 【圖式簡單說明3 (無） 【主要元件符號說明】 (無） 20[Embodiment J] The following examples are for illustrative purposes only and are not to be construed as limiting the invention. EXAMPLES Example 1-3 Preparation of a mixture of methyl pentenoates At atmospheric pressure, the catalyst (Grace-Davison/Davicat SIAL 3501, 21.2 g) The load was loaded into a tubular gas phase reactor and then heated to 255. (: Monitor the reaction temperature in the reactor with a thermometer. Before the introduction of the feed, the desired reaction temperature and pressure are achieved under a nitrogen stream. Controlled by the Brooks mass flow controller to reach the reactor. Gas flow. After reaching the desired conditions, prepare γ-valerolactone solution (1:1 by weight) in dish 6〇11, preheated to 19 〇. 〇 and use ΗΡΙΧΙ feed residual filler Bed f-reactor. At weekly temperature, the product was used for quantitative analysis and analysis by GC. 17 201249536 LHSV wrt-lactone is 0.49. The steaming hall comes from three different running samples. The main ones from these three operations The composition of the fractions is listed in the following table i. There are more than 5 mole % of decyl 2-pentenoate in the total mixture. Table 1 Mixture obtained from gas phase reaction between valerolactone and decyl alcohol % of dimethyl pentenoate in the example MeOH m/m % C-M2P m/m % M4P m/m % tr-M3P m/m % C-M3P m/m % tr-M2P m/m % valerolactone m/m % water m/m % total m/m % 1 1.1 2.2 25.0 44.6 16.3 8.7 1.1 1.1 100 2 0.0 0.8 18.3 48.3 17.5 11.7 0.8 0.8 98 3 0.0 1.6 12.9 48.4 17.7 14.5 1.6 1.6 98 Example methoxycarbonylation of decenoic acid esters α,α'-bis(di-tertiary butylphosphino)-o-di Toluene (20 micromoles, from Strem Chemicals Inc., 15, Rue de I'Atome, ZI, 67800 BISCHHEIM, France); 5 equivalents in 5 ml of sterol The solution was added to the Pd precursor (4 micromoles Pd(OAc)2). Methanesulfonic acid (MSA, 4 microliters, 40 micromoles, 1 equivalent) was added to the catalyst solution, after which the color changed from yellow to orange. Adding a mixture of a substrate (methyl 2-pentenoate, methyl 3-pentenoate, or decyl 2-pentenoate) methyl 3-pentenoate and methyl 4-pentenoate, as in the examples Pre-maid obtained in 1-3 or at a 1:1:1 ratio, and the mixture was moved into a glass insert of Endeavour (8 small pressure steel devices with an upper stirrer) In the tube. The reactor was flushed 5 times with N2, then 10 times with 20 bar of CO. The reactor was pressurized to 20 bar and heated to the indicated reaction temperature. After 1 hour, the reaction vessel was cooled to room temperature and the pressure was released. β 18 201249536 The conversion and selectivity to dimethyl adipate was determined by GC analysis (Table 2). (M2P=2-pentenoic acid decyl ester; M3P=3-methyl glutarate; methyl pentenoate; TOF=update frequency=mole of product obtained per hour per mole of catalyst. Reaction between lactone and decyl alcohol, obtaining a mixture of M2P, M3P and M4P in a gas phase reaction, as described above) Table 2 Hydroxycarbonylation of decenoic acid decyl esters Example substrate temperature (°C) TOF (hour 丨), selectivity of dimethyl ester (%, 4 Μ 2 Ρ 50 105 100' 5 Μ 2 Ρ 75 289 Γ〇〇 6 Μ 2 Ρ 100 417 according to the date of the day of the day Ά 7 from the mixture of Example 1 75 362 ^ yj Example 8 of /ζτ The mixture from Example 2 75 335 loo' 9 From the mixture of Example 3 75 482 97 10 M2P'M3P'M4P (1:1:1) 75 309 100 11 Μ2Ρ'Μ3Ρ>Μ4Ρ (1 :1:1) 100 342 12 Μ3Ρ 50 141 loo Comparative Example 13 Μ3Ρ 75 281 loo ^ 14 Μ3Ρ 100 332 —. Table 2 shows that decyl 2-pentenoate can be used at 50, 75 and 100 ° C with 3 _ Methyl pentenoate actually has the same rate and the same selective conversion. In addition, it contains methyl 2-pentenoate, methyl 3-pentamate and 4-pentenoic acid. The mixture was also converted to methyl adipate at the same rate and selectivity as methyl 3-pentenoate. This experiment shows that a mixture of methyl pentenoate obtained by converting valerolactone can be used in Conversion to dimethyl adipate in the oxycarbonylation reaction, and the presence of methyl 2-pentenoate in this mixture without side effects. Example 13-19 Effect of adding water 19 201249536 α,α' A solution of bis(di-tert-butylphosphino)-o-xylene (40 micromoles, 5 equivalents) in 4 ml of decyl alcohol was added to the Pd precursor (8 micromolar Pd(OAc)2). Anthraquinone sulfonic acid (8 microliters, 80 micromoles, 10 equivalents) was added to the catalyst solution, after which the color was observed to change from yellow to orange. Addition of pentenoic acid ester (6.4 mmol) And water, and the mixture was transferred into a glass Endeavor cannula. The reactor was flushed 5 times with N2, then 10 times with 20 bar of CO. The reactor was pressurized to 20 bar with CO. Heat to the indicated reaction temperature. After 1 hour, the reaction vessel was cooled to room temperature and pressure was released. The conversion was determined by GC analysis. Selective. The exact amount of water is determined by Karl Fisher titration. The results are shown in Table 3. Table 3 Effect of water Example Weight % of water C (%) Selectivity to DMA (% T0F (hour-丨) 13 0.13 75 95 562 14 0.19 78 96 591 15 0.24 79 97 598 16 0.51 78 94 611 17 1.185 75 96 591 18 1.7 70 91 547 19 2.55 68 91 534 [Simple diagram 3 (No ) [Main component symbol description] (none) 20