TWI773190B - Diamine compound and method of preparing the same - Google Patents
Diamine compound and method of preparing the same Download PDFInfo
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本發明係關於一種二胺化合物及其製備方法,特別是關於一種結構穩定的二胺化合物及其製備方法。The present invention relates to a diamine compound and its preparation method, in particular to a structurally stable diamine compound and its preparation method.
在中華民國專利公開第TW201030059A號中,日產化學中原翔一朗等人於2006年申請了一種液晶配向處理劑。此處理劑於摩擦處理時,對膜表面造成之傷痕或刮傷較少,且配向性良好。此處理劑為含有以下結構成分之二胺。 In the Republic of China Patent Publication No. TW201030059A, Nissan Chemical Nakahara Shoichiro et al. applied for a liquid crystal alignment treatment agent in 2006. During the rubbing treatment, the treatment agent causes less scratches or scratches on the film surface and has good orientation. This treating agent is a diamine containing the following structural components.
上述專利中,利用了碳酸雙(4-硝基苯基)來導入脲基,並導入了三乙胺與4-二甲氨基吡啶(DMAP)作為鹼性物質,成功得到帶有二硝基的中間體。再將該中間體與5% Pd/C與1,4-二噁烷混合後,充填氫氣進行還原反應,進而得到二胺基化合物。In the above-mentioned patent, utilize carbonic acid bis(4-nitrophenyl) to import urea group, and import triethylamine and 4-dimethylaminopyridine (DMAP) as basic substance, successfully obtain the urea group with dinitro group. Intermediate. The intermediate is mixed with 5% Pd/C and 1,4-dioxane, and then filled with hydrogen to carry out a reduction reaction, thereby obtaining a diamine compound.
然而,此二胺化合物在作為配向處理劑時,在反應過程中化合物中所含的-N-CO-N-容易被破壞,產生多種副產物,而這些副產物的存在也會對液晶面板的品質造成影響。However, when the diamine compound is used as an alignment treatment agent, the -N-CO-N- contained in the compound is easily destroyed during the reaction process, resulting in a variety of by-products, and the existence of these by-products will also affect the LCD panel. quality affects.
故,有必要提供一種二胺化合物及其製備方法,該二胺化合物具有較好的結構穩定性,在配向反應發生時減少副產物的生成,以解決習用技術中所存在的問題。Therefore, it is necessary to provide a diamine compound and a preparation method thereof. The diamine compound has better structural stability and reduces the generation of by-products when the alignment reaction occurs, so as to solve the problems existing in the conventional technology.
本發明之主要目的在於提供一種的二胺化合物及其製備方法,可獲得帶有烷基的二胺化合物,利用烷基保護二胺化合物中-N-CO-N-的鏈結,使其在配向反應過程中不被破壞,可以減少不同種類副產物的產生。同時,該二胺化合物的製備方法也具有相當優良的產率。The main purpose of the present invention is to provide a diamine compound and a preparation method thereof, which can obtain a diamine compound with an alkyl group, and use the alkyl group to protect the -N-CO-N- link in the diamine compound to make it in the diamine compound. The alignment reaction process is not destroyed, which can reduce the generation of different kinds of by-products. At the same time, the preparation method of the diamine compound also has quite good yield.
為達上述之目的,本發明的一實施例提供一種二胺化合物的製備方法,其包含步驟: (1) 混合N-R-2-(4-硝基苯基)乙胺鹽酸鹽與一溶劑,形成一反應液; (2) 在該反應液中加入一鹼性物,使該反應液呈鹼性; (3) 在該反應液中加入三光氣,合成二硝基化合物;以及 (4) 將該二硝基化合物進行一還原反應,形成二胺化合物,其中該二胺化合物具有如下式(I)所示的結構: ……(I), 其中R是甲基或乙基。 To achieve the above purpose, an embodiment of the present invention provides a method for preparing a diamine compound, which comprises the steps of: (1) mixing NR-2-(4-nitrophenyl)ethanamine hydrochloride and a solvent, forming a reaction solution; (2) adding an alkaline substance to the reaction solution to make the reaction solution alkaline; (3) adding triphosgene to the reaction solution to synthesize dinitro compounds; and (4) adding The dinitro compound undergoes a reduction reaction to form a diamine compound, wherein the diamine compound has the structure shown in the following formula (I): ...(I), wherein R is methyl or ethyl.
在本發明的一實施例中,該溶劑是二氯甲烷、甲苯、二甲苯、四氫呋喃或1,4-二噁烷。In one embodiment of the present invention, the solvent is dichloromethane, toluene, xylene, tetrahydrofuran or 1,4-dioxane.
在本發明的一實施例中,R是甲基。In one embodiment of the invention, R is methyl.
在本發明的一實施例中,該鹼性物是氫氧化鈉、碳酸鉀、二異丙基乙胺、4-二甲氨基吡啶、三乙胺或其混合物。In one embodiment of the present invention, the basic substance is sodium hydroxide, potassium carbonate, diisopropylethylamine, 4-dimethylaminopyridine, triethylamine or a mixture thereof.
在本發明的一實施例中,該二硝基化合物具有如下式(II)所示的結構: …….式(II)。 In one embodiment of the present invention, the dinitro compound has the structure shown in the following formula (II): .... formula (II).
在本發明的一實施例中,該還原反應是使用一催化劑及一還原劑,將該二硝基化合物的硝基(-NO 2)還原成胺基(-NH 2)。 In an embodiment of the present invention, the reduction reaction uses a catalyst and a reducing agent to reduce the nitro group (-NO 2 ) of the dinitro compound to an amine group (-NH 2 ).
在本發明的一實施例中,該催化劑是Pd/C、氧化鉑、鐵粉或氯化錫。In one embodiment of the present invention, the catalyst is Pd/C, platinum oxide, iron powder or tin chloride.
在本發明的一實施例中,該還原劑是氫氣、聯胺、氯化氫或氯化銨。In one embodiment of the present invention, the reducing agent is hydrogen, hydrazine, hydrogen chloride or ammonium chloride.
本發明的另一實施例提供一種二胺化合物,具有如下式(I)所示的結構: ……(I), 其中R是甲基或乙基。 Another embodiment of the present invention provides a diamine compound having the structure shown in the following formula (I): ...(I), wherein R is methyl or ethyl.
在本發明的一實施例中,R是甲基。In one embodiment of the invention, R is methyl.
為了讓本發明之上述及其他目的、特徵、優點能更明顯易懂,下文將特舉本發明較佳實施例,作詳細說明如下。本發明所提到的單數形式“一”、“一個”和“所述”包括複數引用,除非上下文另有明確規定。例如,術語“一化合物”或“至少一種化合物”可以包括多個化合物,包括其混合物;本發明文中提及的「%」若無特定說明皆指「重量百分比(wt%)」;數值範圍(如10%~11%的A)若無特定說明皆包含上、下限值(即10%≦A≦11%);數值範圍若未界定下限值(如低於0.2%的B,或0.2%以下的B),則皆指其下限值可能為0(即0%≦B≦0.2%);各成份的「重量百分比」之比例關係亦可置換為「重量份」的比例關係。上述用語是用以說明及理解本發明,而非用以限制本發明。In order to make the above-mentioned and other objects, features and advantages of the present invention more clearly understood, the preferred embodiments of the present invention will be exemplified below, and will be described in detail as follows. References herein to the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. For example, the term "a compound" or "at least one compound" may include multiple compounds, including mixtures thereof; the "%" mentioned in the present invention refers to "weight percent (wt%)" unless otherwise specified; the numerical range ( For example, 10% to 11% of A) includes upper and lower limits unless otherwise specified (ie 10%≦A≦11%); if the value range does not define the lower limit (such as B below 0.2%, or 0.2 % below B), it means that the lower limit may be 0 (ie 0%≦B≦0.2%); the proportional relationship of “weight percent” of each component can also be replaced by the proportional relationship of “weight part”. The above terms are used to describe and understand the present invention, but not to limit the present invention.
本發明的一實施例提供一種二胺化合物的製備方法,其包含步驟:(S1)混合N-R-2-(4-硝基苯基)乙胺鹽酸鹽與一溶劑,形成一反應液;(S2)在該反應液中加入一鹼性物,使該反應液呈鹼性;(S3)在該反應物中加入三光氣,合成二硝基化合物;以及(S4)將該二硝基化合物進行一還原反應,形成二胺化合物。An embodiment of the present invention provides a method for preparing a diamine compound, which comprises the steps of: (S1) mixing N-R-2-(4-nitrophenyl)ethylamine hydrochloride and a solvent to form a reaction solution; ( S2) adding a basic substance to the reaction solution to make the reaction solution alkaline; (S3) adding triphosgene to the reaction solution to synthesize a dinitro compound; and (S4) carrying out the dinitro compound A reduction reaction forms a diamine compound.
本發明將於下文逐一詳細說明上述各步驟的實施細節及其原理。The present invention will hereinafter describe in detail the implementation details and principles of the above steps one by one.
本發明一實施例之二胺化合物的製備方法首先是:(S1)混合N-R-2-(4-硝基苯基)乙胺鹽酸鹽與一溶劑,形成一反應液。在本步驟中,該溶劑是二氯甲烷、甲苯、二甲苯、四氫呋喃或1,4-二噁烷。較佳的,R是一烷基,可例如是甲基或乙基。The preparation method of the diamine compound according to an embodiment of the present invention is firstly: (S1) mixing N-R-2-(4-nitrophenyl)ethylamine hydrochloride and a solvent to form a reaction solution. In this step, the solvent is dichloromethane, toluene, xylene, tetrahydrofuran or 1,4-dioxane. Preferably, R is an alkyl group, which can be, for example, methyl or ethyl.
本發明一實施例之二胺化合物的製備方法接著是:(S2)在該反應液中加入一鹼性物,使該反應液呈鹼性。在本步驟中,該鹼性物是氫氧化鈉、碳酸鉀、二異丙基乙胺、4-二甲氨基吡啶、三乙胺或其混合物。例如,可使用三乙胺與4-二甲氨基吡啶以一適當比例混合成適合進行反應的鹼性環境,但並不限於此兩種物質。The preparation method of the diamine compound according to an embodiment of the present invention is followed by: (S2) adding a basic substance to the reaction solution to make the reaction solution alkaline. In this step, the basic substance is sodium hydroxide, potassium carbonate, diisopropylethylamine, 4-dimethylaminopyridine, triethylamine or a mixture thereof. For example, triethylamine and 4-dimethylaminopyridine can be mixed in an appropriate ratio to form an alkaline environment suitable for the reaction, but it is not limited to these two substances.
本發明一實施例之二胺化合物的製備方法接著是:(S3)在該反應液中加入三光氣,合成二硝基化合物。在本步驟中,該二硝基化合物具有如下式(II)所示的結構: ……(II) The preparation method of the diamine compound according to an embodiment of the present invention is as follows: (S3) adding triphosgene to the reaction solution to synthesize a dinitro compound. In this step, the dinitro compound has the structure shown in the following formula (II): ...(II)
本發明一實施例之二胺化合物的製備方法接著是:(S4)將該二硝基化合物進行一還原反應,形成二胺化合物。該二胺化合物具有如下式(I)所示的結構: ……(I) The method for preparing a diamine compound according to an embodiment of the present invention is followed by: (S4) performing a reduction reaction on the dinitro compound to form a diamine compound. The diamine compound has the structure shown in the following formula (I): ...(I)
上述式(I)中,R是甲基或乙基。較佳的,R是甲基。通過甲基的保護,該二胺化合物中的N-C-N健結不易被破壞,可使整體分子結構穩定,在使用作為配向反應物時可減少副產物的產生。In the above formula (I), R is a methyl group or an ethyl group. Preferably, R is methyl. Through the protection of the methyl group, the N-C-N bond in the diamine compound is not easily destroyed, the overall molecular structure can be stabilized, and the generation of by-products can be reduced when used as an alignment reactant.
在本步驟中,該還原反應可使用一催化劑及一還原劑,將該二硝基化合物的硝基(-NO 2)還原成胺基(-NH 2)。在一實施例中,該催化劑可例如是Pd/C、氧化鉑、鐵粉或氯化錫,以及該還原劑可例如是氫氣、聯胺、氯化氫或氯化銨。較佳的,該催化劑為Pd/C且該還原劑為氫氣。較佳的,該催化劑為Pd/C且該還原劑為聯胺。 In this step, the reduction reaction can use a catalyst and a reducing agent to reduce the nitro group (-NO 2 ) of the dinitro compound to an amine group (-NH 2 ). In one embodiment, the catalyst may be, for example, Pd/C, platinum oxide, iron powder, or tin chloride, and the reducing agent may be, for example, hydrogen, hydrazine, hydrogen chloride, or ammonium chloride. Preferably, the catalyst is Pd/C and the reducing agent is hydrogen. Preferably, the catalyst is Pd/C and the reducing agent is hydrazine.
本發明的另一實施例提供一種二胺化合物,具有如下式(I)所示的結構: ……(I), 其中R是甲基或乙基。較佳的,R是甲基。 Another embodiment of the present invention provides a diamine compound having the structure shown in the following formula (I): ...(I), wherein R is methyl or ethyl. Preferably, R is methyl.
為使本發明之二胺化合物及其製備方法更明確且易於了解,請參考下述實際操作流程,但其並非用以限制本發明之二胺化合物的結構及其製備方法中所包含的各個步驟。In order to make the diamine compound of the present invention and the preparation method thereof clearer and easier to understand, please refer to the following actual operation process, but it is not intended to limit the structure of the diamine compound of the present invention and each step included in the preparation method thereof .
實施例1:合成二硝基化合物Example 1: Synthesis of dinitro compounds
反應機制如下: The reaction mechanism is as follows:
首先,將95.0克的N-甲基-2-(4-硝基苯基)乙胺鹽酸鹽裝入反應瓶內,並加入665毫升CH 2Cl 2後,攪拌均勻。接著,在前述混合溶液加入8.92克的4-二甲氨基吡啶(DMAP)後,慢慢滴加88.66克的三乙胺,此為反應溶液A。 First, 95.0 g of N-methyl-2-(4-nitrophenyl)ethanamine hydrochloride was charged into the reaction flask, and 665 ml of CH 2 Cl 2 was added, followed by stirring uniformly. Next, after adding 8.92 g of 4-dimethylaminopyridine (DMAP) to the aforementioned mixed solution, 88.66 g of triethylamine was slowly added dropwise, and this was the reaction solution A.
將9克的固體三光氣投入等壓滴定漏斗內,加115毫升CH 2Cl 2搖晃至全溶,此為反應溶液B。 Put 9 grams of solid triphosgene into the isobaric titration funnel, add 115 ml of CH 2 Cl 2 and shake until it is completely dissolved, this is the reaction solution B.
將前述反應溶液B在1小時內滴入反應溶液A中,並以冰浴控制於室溫。The aforementioned reaction solution B was dropped into the reaction solution A within 1 hour, and was controlled to room temperature with an ice bath.
重複配製反應溶液B並滴入反應溶液A兩次,最後一次所配製的反應溶液B時,三光氣減量至8克,CH 2Cl 2減量至95毫升。滴加完成後再維持室溫反應1小時。 Repeated preparation of reaction solution B and dropwise addition of reaction solution A twice. When the last prepared reaction solution B was prepared, the amount of triphosgene was reduced to 8 g, and the amount of CH 2 Cl 2 was reduced to 95 ml. After the dropwise addition was completed, the reaction was maintained at room temperature for 1 hour.
利用減壓濃縮去除過多的CH 2Cl 2後,加入3公升正己烷(n-Hexane),可析出淡橘色粉體。過濾後,加入1公升水攪拌,去除三乙胺鹽酸鹽。再過濾一次,取出粉體以烘箱烘乾,得68.0克淡橘色粉體為二硝基化合物,產率是80.3%。 After the excess CH 2 Cl 2 was removed by concentration under reduced pressure, 3 liters of n-Hexane was added to precipitate a pale orange powder. After filtration, 1 liter of water was added and stirred to remove triethylamine hydrochloride. After filtering again, the powder was taken out and dried in an oven to obtain 68.0 g of light orange powder as a dinitro compound with a yield of 80.3%.
1H-NMR (500MHz, DMSO-d6, δ ppm): 8.15 (m, 2H), 7.34 (d, 2H), 3.40 (t, 2H), 2.95 (t, 2H), 2.74 (s, 3H). 1 H-NMR (500MHz, DMSO-d6, δ ppm): 8.15 (m, 2H), 7.34 (d, 2H), 3.40 (t, 2H), 2.95 (t, 2H), 2.74 (s, 3H).
實施例2:合成二胺化合物Example 2: Synthesis of Diamine Compounds
反應機制如下: The reaction mechanism is as follows:
首先,取上述二硝基化合物68.0克,裝入1公升反應瓶內,再加入150毫升乙醇(EtOH)攪拌均勻。接著加入催化劑6.8克的Pd/C,加熱至迴流,然後慢慢滴入88克的80%聯胺(Hydrazine),滴完後再迴流1小時。First, take 68.0 g of the above-mentioned dinitro compound, put it into a 1-liter reaction flask, and then add 150 ml of ethanol (EtOH) and stir evenly. Then add catalyst 6.8 g of Pd/C, heat to reflux, then slowly drop 88 g of 80% hydrazine (Hydrazine), and then reflux for 1 hour after dropping.
過濾以移除碳鈀觸媒(Pd/C),並將過濾液減壓濃縮,可得49.5克的米黃色粉體,產率86.2%。經NMR判斷可知為目標產物二胺化合物 。 Filtration was performed to remove the palladium-carbon catalyst (Pd/C), and the filtrate was concentrated under reduced pressure to obtain 49.5 g of beige powder with a yield of 86.2%. It is determined by NMR that it is the target product diamine compound .
1H-NMR (500MHz, CDCl3, δ ppm): 6.95 (d, 2H), 6.59 (d, 2H), 3.56 (s, 2H), 3.28 (m, 2H), 2.73 (s, 3H) , 2.70 (m, 2H). 1 H-NMR (500MHz, CDCl3, δ ppm): 6.95 (d, 2H), 6.59 (d, 2H), 3.56 (s, 2H), 3.28 (m, 2H), 2.73 (s, 3H) , 2.70 ( m, 2H).
比較例1:碳酸雙(4-硝基苯基)與N-甲基-2-(4-硝基苯基)乙胺鹽酸鹽的反應Comparative Example 1: Reaction of bis(4-nitrophenyl) carbonate with N-methyl-2-(4-nitrophenyl)ethanamine hydrochloride
由於為了製備具有烷基保護的二胺化合物,中間體二硝基化合物的合成是相當重要的。根據中華民國專利公開第TW201030059A號中,日產化學中原翔一朗等人所採用的方法,設計反應機制如下: Since in order to prepare diamine compounds with alkyl protection, the synthesis of intermediate dinitro compounds is quite important. According to the method adopted by Nissan Chemical Nakahara Shoichiro et al. in Patent Publication No. TW201030059A of the Republic of China, the designed reaction mechanism is as follows:
採取的實驗步驟如下:The experimental steps taken are as follows:
首先,將3.0克的N-甲基-2-(4-硝基苯基)乙胺鹽酸鹽與2.0克的碳酸雙(4-硝基苯基)裝入瓶內,並加入25毫升CH 2Cl 2後,攪拌均勻。此為反應溶液C。在反應溶液C中加入0.16克的DMAP後,慢慢滴加4.0克三乙胺。滴加完成後以TLC追蹤反應,待觀測無起始物後,加水析出產物。過濾後,得到淡橘色粉體。經鑑定後,此產物為不明混合物,並非所預定的目標產物(二硝基化合物)。 First, 3.0 g of N-methyl-2-(4-nitrophenyl)ethanamine hydrochloride and 2.0 g of bis(4-nitrophenyl) carbonate were charged into a bottle, and 25 ml of CH After 2 Cl 2 , stir well. This is reaction solution C. After adding 0.16 g of DMAP to the reaction solution C, 4.0 g of triethylamine was slowly added dropwise. After the dropwise addition was completed, the reaction was followed by TLC, and after no starting material was observed, water was added to separate out the product. After filtration, a pale orange powder was obtained. After identification, this product is an unknown mixture, not the intended target product (dinitro compound).
從比較例1的結果可知,帶有甲基的二硝基化合物無法通過上述反應機制合成成功。也就是說,將反應物的-NH 2鹽酸鹽以甲基取代H後,二硝基化合物無法被合成成功。 As can be seen from the results of Comparative Example 1, the dinitro compound having a methyl group could not be successfully synthesized by the above-mentioned reaction mechanism. That is to say, after the -NH 2 hydrochloride of the reactant is replaced by a methyl group, the dinitro compound cannot be successfully synthesized.
相較於先前技術,本發明所提供的二胺化合物及其製備方法,使用烷基保護二胺化合物中的N-CO-N鍵結,使整體結構穩定,當使用作為配向反應物時,N-CO-N鍵結不容易被破壞,故可減少副產物的產生,使液晶面板的液晶組成較為單純,有助於面板品質的提升。Compared with the prior art, the diamine compound and its preparation method provided by the present invention use an alkyl group to protect the N-CO-N bond in the diamine compound to stabilize the overall structure. When used as an alignment reactant, N The -CO-N bond is not easily destroyed, so the generation of by-products can be reduced, the liquid crystal composition of the liquid crystal panel is relatively simple, and the quality of the panel is improved.
雖然本發明已以較佳實施例揭露,然其並非用以限制本發明,任何熟習此項技藝之人士,在不脫離本發明之精神和範圍內,當可作各種更動與修飾,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。Although the present invention has been disclosed with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications 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 appended patent application.
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