五、發明説明（ A7 B7 (1)發明背景 1,1’-二烷基-4,4’-聯吡啶鹽為習知的除草劑，其中R = CH3，X=CI時即為最有名的農藥原體巴拉刈（）， 結構如第一圖所示。 r_n〇^〇+r 2X- 經濟部中央搮準局Μζ工消费合作社印裝 第一圖 利用氛化物催化1-烷基咕啶鹽（Laiky丨pyr1d|niUm salt)進行偶合反應後，再經由氧化來製造 聯吡啶鹽是個公開的合成方法。但是關於如何除去殘餘過 篁氰化物與反應產生之無機鹽’至今尚無低污染的處理方 法被報導。美國第 3,723,444; 3,787,426; 3,868,381; 3,899,500; 3,905986 號專利曾揭示在含5_5〇% 水之有機溶劑，利用1-烧基纸啶鹽與易溶解型的酸接收劑 (係指氫氧化鈉）在至少二當量以上之氰化納存在下進行 反應，再經氧化後可製造1,1，-二提基_4,4’-聯吡啶鹽，等缺 點是製程中除去殘餘過量氰化物與反應產生之無機鹽之方 法不經濟且效果較差，例如在上述專利之實施例中曾提及 利用4,4 一胺基-一本乙婦-2,2’_二續酸（amsonic acid)之 可溶性鹼金屬鹽’將1,1’-二烷基-4,4，-聯吡啶鹽陽離子以其 酸鹽形式沈澱，再以過濾方式與氰化物分離，此酸鹽中所5. Description of the invention (A7 B7 (1) Background of the invention 1,1'-dialkyl-4,4'-bipyridine is a conventional herbicide, where R = CH3 and X = CI are the most famous The structure of the pesticide precursor Balazone () is shown in the first picture. R_n〇 ^ 〇 + r 2X- Printed by the Central Economic and Trade Standards Bureau of the Ministry of Economic Affairs, Mζ Industrial and Consumer Cooperatives. After the coupling reaction of the salt (Laiky 丨 pyr1d | niUm salt), the bipyridyl salt is produced by oxidation. However, there is no low-contamination method on how to remove residual percyanide and the inorganic salt produced by the reaction. The treatment method is reported. U.S. Patent Nos. 3,723,444; 3,787,426; 3,868,381; 3,899,500; 3,905986 have disclosed that organic solvents containing 5-50% water, using 1-carbon-based paper pyridinium salt and easily soluble acid acceptor (system (Referring to sodium hydroxide) in the presence of at least two equivalents of sodium cyanide, and then oxidized to produce 1,1, -ditidyl-4,4'-bipyridine salt, etc. The disadvantage is that the residue is removed during the process The method of excessive cyanide and inorganic salt produced by the reaction is uneconomical and ineffective, such as In the examples of the aforementioned patents, it has been mentioned that the use of a soluble alkali metal salt of 4,4-monoamino-one aceto-2,2'-amsonic acid '1,1'-dialkyl -4,4, -bipyridine salt cation is precipitated as its acid salt, and then separated from cyanide by filtration.
私紙張尺度適用中國國家揉隼（CNS ) A4规格（210X 第5頁 (請先Μ讀背面之注意事項再填寫本頁) 裝· 訂 線 A7 B7 五、發明説明（2 ) 殘留的氰離子，可經由陰離子交換分離處理後得到合格的 商品，其處理程序較繁複，成本也較高。另一例則是在1,1’-二烷基_4,4’-聯吡啶鹽陽離子水溶液中加入硫酸亞鐵水合物 沈澱氰化物而後過濾之，但是這種方法會破壞產品之安定 性。另一例則揭露以甲苯等有機溶劑萃取偶合後之1J，-二 烷基-4,4’-聯吡啶鹽之前驅物，將過量之氰離子留在水中， 收集有機層氧化得到1,1’-二烷基-4,4’-聯吡啶鹽，這種方法 收率明顯偏低，並且面臨其水層氰離子之處理的困難。因 此，發明一種無氰離子且低含鹽量的1,1，_二烷基-4,4’-聯吡 啶鹽之改良製程，走個具有產業利用性之課題。 (2)發明概述 本發明係揭示一種聯吡啶鹽的改良製法，其特點是在 一種低含水量的有機溶劑中將適量的固體型酸接收劑與鹼 金屬氰化物混合，形成低溶解度之混合型催化劑，用於催 化1 -烷基祀啶鹽進行偶合反應以生成1,1，-二烷基-4,4’ ·聯吡 •咬鹽之前軀物，中和反應過程所產生之酸及吸附反應生成 之水所形成之金屬鹽混合物，利用熱過濾可與1,1，-二烷基-4,4’-聯吡啶鹽之前驅物分離，所收集之濾液經濃縮後得到之 藍黑色固體，再經氧化即得到無氰離子且低含鹽量的11’ -二烷基-4,4’-聯吡啶鹽。 比較傳統方法（使用過量氰化鈉作為催化劑）而言， 本發明所使用之混合型催化劑（含氰化物）之安定性與有 本紙張尺度逋用中國國家揉準（CNS ) A4规格（210 ----------^-- (請先閲讀背面之注意事項再填寫本頁) 、π 線 .¼濟部中夬棣準局貝工消费合作社印褽 A7The size of the private paper is applicable to the Chinese national standard (CNS) A4 (210X page 5 (please read the precautions on the back before filling this page). Binding line A7 B7 5. Description of the invention (2) Residual cyanide ions, Qualified products can be obtained after anion exchange separation and treatment, the processing procedure is more complicated and the cost is higher. Another example is adding sulfuric acid to the 1,1'-dialkyl_4,4'-bipyridine salt cation aqueous solution Ferrous hydrate precipitates cyanide and then filters it, but this method will damage the stability of the product. Another example revealed the extraction of 1J, -dialkyl-4,4'-bipyridine salt after coupling with an organic solvent such as toluene. The precursors left excess cyanide ions in the water and collected the organic layer for oxidation to obtain 1,1'-dialkyl-4,4'-bipyridine salt. This method has a significantly lower yield and faces its water layer. Difficulties in the treatment of cyanide ions. Therefore, an improved process for inventing a 1,1, _dialkyl-4,4'-bipyridine salt without cyanide ions and low salt content was devised to solve the problem of industrial applicability. (2) Summary of the invention The present invention discloses an improved method for preparing bipyridine salt. It is characterized by mixing an appropriate amount of a solid acid receiver with an alkali metal cyanide in an organic solvent with a low water content to form a low-solubility mixed catalyst for catalyzing the coupling reaction of a 1-alkyl pyridinium salt to produce 1 , 1, -Dialkyl-4,4 '· bipyridine • Pre-bite, metal salt mixture formed by neutralizing the acid produced by the reaction process and the water produced by the adsorption reaction, can be used with 1, The 1, -dialkyl-4,4'-bipyridine salt precursor was separated, and the collected filtrate was concentrated to obtain a blue-black solid, which was then oxidized to obtain 11 '-without cyanide ion and low salt content. Dialkyl-4,4'-bipyridine salt. Compared with the traditional method (using excess sodium cyanide as catalyst), the stability of the mixed catalyst (containing cyanide) used in the present invention is as good as the paper size. Use Chinese National Standard (CNS) A4 (210 ---------- ^-(Please read the notes on the back before filling out this page), π line. Pui Gong Consumer Cooperative Neem A7
、發明説明（ 經濟部中央揉準局I工消费合作社印策 效度較佳，明顯減少了製程中氛化物之使用量，並且在反 應後以固體形式回收副產物（金屬鹽水合物）與低溶解性 之氰化物’本製程避免了廢水的產生。換而言之，本發明 提供一種無氰離子且低含鹽量的彳，彳，-二烷基_ 44，_聯吡啶鹽 之改良製程。 ⑶發明的詳細說明 本發明提供一種無氰離子且低含鹽量的H，-二烷基_ 4,4’-聯吡啶鹽芝改良製程。詳細說明技術内容，係在一種低 含水量的有機溶劑（係指含水率低於5%之醇類有機溶劑） ，將適量的固體型酸接收劑（係指鹼土族金屬氧化物）與 驗金屬氰化物鹿合製備成一種低溶解度之混合型催化劑， 加入1-炫基咬鹽進行偶合反應’可以有效的生成11, _二 烧基-4,4’-聯吼咬鹽的前驅物，過程中該混合型催化劑可以 中和反應過程所產生之酸’並且吸附反應生成之水，形成 一種混合的金屬鹽永合物’反應完成後利用趁熱過濾將含 鹽之氰化物與1,1’-二炫基-4,4’-聯牝咬鹽之前驅物分離，收 集其濾、液蒸館回收溶劑後可得到該前驅物，再依熟知之氧 ;化方法進行氧化（例如加水通入氣氣，或以鹽酸調整酸驗 值同時通入空氣等），可以直接產生不含氰離子且低含鹽 量之1,1’-二烷墓-4,4，-聯吡啶鹽的水溶液，此產品係一種殺 草劑，本製程所製造之樣品規格符合市場要求。、 Explanation of the invention (The validity of the printing policy of the I Industrial Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs is better, which significantly reduces the amount of atmosphere used in the process, and recovers by-products (metal salt hydrates) and Soluble cyanide This process avoids the generation of waste water. In other words, the present invention provides an improved process for hydrazone, hydrazone, -dialkyl_44, _bipyridine salt without cyanide ion and low salt content. (3) Detailed description of the present invention The present invention provides an improved process for H, -dialkyl-4,4'-bipyridine salted salt without cyanide ion and low salt content. The technical content is described in detail in a low water content Organic solvents (referring to alcoholic organic solvents with a moisture content of less than 5%). An appropriate amount of solid acid receiver (referring to alkaline earth metal oxides) and metal cyanide deer are combined to prepare a low solubility mixed type. Catalyst, adding 1-Hexyl bite salt for coupling reaction can effectively generate the precursor of 11, _dioxo-4,4'-synthetic bite salt, and the mixed catalyst can neutralize the produced in the process Acid The water should be formed to form a mixed metal salt permanent compound. After the reaction is completed, the salt-containing cyanide is separated from the 1,1'-dixyl-4,4'-bipyridine precursor by hot filtration. The precursor can be obtained after collecting the filter and recovering the solvent in the liquid steaming hall, and then oxidizing according to the well-known oxygen; chemical methods (such as adding water to air, or adjusting the acid test value with hydrochloric acid while passing air). Directly produces an aqueous solution of 1,1'-dioxane-4,4, -bipyridine salt without cyanide ions and low salt content. This product is a herbicide. The sample specifications produced by this process meet market requirements. .
本改良方法可以通式[C5H5N+-R]X-(或[C5H5N+RI2Y2-J 偶合成（C5H4M-R)2，表示如下： 私紙張尺度適用中國國家揉準（CNS ) Λ4规格（210> 第7頁 ----------^------II-------0 (請先Η讀背面之注意事項再填寫本頁) 393480 五、發明説明（4 ) A7 B7 2[C5H5N+-RJX- 催化量氱化物siiiirThis improved method can be generalized as [C5H5N + -R] X- (or [C5H5N + RI2Y2-J even-synthesized (C5H4M-R) 2], and is expressed as follows: Private paper standards are applicable to Chinese National Standards (CNS) Λ4 specifications (210 > Page 7 ---------- ^ ------ II ------- 0 (Please read the precautions on the back before filling out this page) 393480 V. Description of the invention (4) A7 B7 2 [C5H5N + -RJX- catalytic
(C5H4N-R)2 + 2HX 請 βϋ 閲 進步說月本發明所用1-燒基敗咬盟[c5h5n+-r]x_ 1 (或㈣5㈣】2丫 2.)之R係指*M。個碳的脂肪键，X# 才曰Cl，Br，I，HS〇4，γ係指s〇4 ;所用之驗金屬氣化物係 f 氛彳!^等（較佳者為氛化納），其使用量在0·2 (較佳者為〇·3至1.〇當量）；固體赚接 鋇等二較佳者為氧鄉其適當之使用量 H虽置之間（較佳者為〇·8至1.2當量）；有機溶劑係指 醇類溶劑’例如甲醇、乙醇、異丙醇、乙二醇及三甘油醇 (Tnethlene-glycoi)等（較佳者為甲醇）；低含水率係指溶 劑之含水率在〇.1%至5%間（較佳者為0·1。/。至1%);而 所合成之1,1’-二院基_4,4，_聯呢々鹽之前_ (^切叫 之烷基係指1_1〇個碳的贿鏈；輯合成之彳」，二燒基_ 4,4 -聯呢咬鹽之烧基係指no個碳的脂肪鏈，鹽係指氣 鹽、溴鹽、碘鹽、硫酸氫鹽與硫酸鹽，特別是指^，·二甲 基Ά聯吡啶氣鹽》 下述之具體實施例是用來詳細說明本發明之目的、特 徵及功效，對於熟悉此類技藝之人仕而言，根據上述說明 本紙張尺度逍用中國國家揉準（CNS ) Α4規格（210:第8頁 面 之 注(C5H4N-R) 2 + 2HX Please read βϋ. Progress means that the 1-alkyl radical [c5h5n + -r] x_ 1 (or ㈣5㈣) 2_ used in the present invention refers to * M. A carbon fatty bond, X # is called Cl, Br, I, HS〇4, γ refers to s〇4; the metal gasification system used is f 彳 ^! ^ Etc. (preferably 氛 Na) The amount used is between 0.2 (preferably 0.3 to 1.0 equivalent); the two preferred ones, such as solid barium, are oxygen, and the appropriate amount H is used (the better is 〇 · 8 to 1.2 equivalents); organic solvents refer to alcoholic solvents such as methanol, ethanol, isopropanol, ethylene glycol, and Tnethlene-glycoi (preferably methanol); low water content refers to solvents The water content is between 0.1% and 5% (preferably from 0.1% to 1%); and the synthesized 1,1'-two-yuan base _4,4, _lianfasium salt Before _ (^ cut-called alkyl refers to a bridging chain of 1-10 carbons; the synthesis of 彳 ， ", dialkyl group 4, 4, -biphenyl salt refers to a fatty chain of no carbon, salt Refers to gas salts, bromine salts, iodide salts, hydrogen sulfate salts, and sulfate salts, especially ^, · dimethylpyridine bipyridine gas salts. The following specific examples are used to explain the purpose and characteristics of the present invention in detail. And effects, for those who are familiar with such skills, according to the above description Xiao with China National Paper-scale quasi-rub (CNS) Α4 Specifications (210: 8 pages of Notes
I 旁 經濟部中央揉準局負工消费合作社印製 經濟部中央揉準局工消费合作社印装 393480 a? _B7 五、發明説明（5 ) ，可能對該具體實施例作部份變更及修改，而並不脫離出 本發明之精神範疇，所以本創作之專利保護範圍僅由所附 申請專利範圍來加以說明。 實施例一至六 室溫下在1L反應瓶中放入曱醇(500 mL，含水率為 0.5%)，氰化鈉（11.8 g，0.241 莫耳），氧化鈣（27.0g，0.482 莫耳‘），攪拌一小時後陸續加入1-甲基敗啶氣鹽(62.0g， 0.479莫耳），過程加熱至60±5。。並維持兩小時，内容物 趁熱將曱醇溶液以氮氣加壓經過多孔性濾頭過濾，收集深 藍色不透明濾液於另一個反應瓶，並回收白色固體（約75 g)留於原反應瓶中。濾液經減壓蒸镏回收85%甲醇（>425 mL)後，冷卻至5至10°C並維持一小時，過濾、乾燥得到藍 黑色結晶性粉末（即1,1’·二曱基-4,4’-聯吡啶鹽之前驅物） ’加入水（70 ml)並在室溫下通入氣氣至内容物呈淡黃色， 其pH為4至6。得到黃綠色油狀溶液135g (UV定量A.I.為 ，收率92%。IR(溴化鉀)λ3442,3054, 3019, 2994， 2966, 2857, 1640, 1561, 1507, 1465,1438, 1356, 1269， 1235,1180, 815 cnr1 ； 1 HNMR (300 MHz, D20) d 9.07 (d, 4H, J = 6.6 Hz), 8.55 (d, 4H, J = 6.6 Hz), 4.82 (s, 6 H)； MS (EI+，m/e，相對強度）186 (M+，20%), 171 (M+-CH3， 76%)，156 (M+-2CH3,100%)。IR，NMR，MS圖譜與預期 產物二甲基-4,4’-聯吡啶氣鹽）相符。分析内容物中 本纸張尺度遥用中國國家橾準（CNS ) A4规格（210 _ 9 ¥ *" --- ---------.—^------訂 1^---1--^ (請先閱讀背面之注意事項再填寫本頁) 五、發明説明（6 ) 不含氰離子。過財所两之近I Printed by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs and Consumer Cooperatives Printed by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs and Consumer Cooperatives 393480 a? _B7 V. Description of the Invention (5), some changes and modifications may be made to this specific embodiment. Without departing from the spirit of the present invention, the scope of patent protection for this creation is only explained by the scope of the attached patent application. Examples 1 to 6 Put methanol (500 mL, 0.5% water content), sodium cyanide (11.8 g, 0.241 mol), calcium oxide (27.0 g, 0.482 mol ') in a 1L reaction bottle at room temperature. After stirring for one hour, 1-methylpiridine gas salt (62.0g, 0.479 mole) was successively added, and the process was heated to 60 ± 5. . Keep it for two hours. The content is filtered while the methanol solution is pressurized with nitrogen through a porous filter while hot. The dark blue opaque filtrate is collected in another reaction flask, and the white solid (about 75 g) is recovered and left in the original reaction flask. . The filtrate was evaporated under reduced pressure to recover 85% methanol (> 425 mL), cooled to 5 to 10 ° C and maintained for one hour, filtered, and dried to obtain a blue-black crystalline powder (that is, 1,1'-diamidyl- Precursor of 4,4'-bipyridine salt) 'Add water (70 ml) and aerate at room temperature until the contents are pale yellow, with a pH of 4 to 6. 135 g of yellow-green oily solution was obtained (quantitative UV AI was 92% yield. IR (potassium bromide) λ3442,3054, 3019, 2994, 2966, 2857, 1640, 1561, 1507, 1465, 1438, 1356, 1269, 1235,1180, 815 cnr1; 1 HNMR (300 MHz, D20) d 9.07 (d, 4H, J = 6.6 Hz), 8.55 (d, 4H, J = 6.6 Hz), 4.82 (s, 6 H); MS ( EI +, m / e, relative intensity) 186 (M +, 20%), 171 (M + -CH3, 76%), 156 (M + -2CH3, 100%). IR, NMR, MS spectrum and expected product dimethyl- 4,4'-bipyridine gas salt). The paper content in the analysis content is remotely used in China National Standards (CNS) A4 specifications (210 _ 9 ¥ * " --- ---------.— ^ ------ Order 1 ^ --- 1-^ (Please read the notes on the back before filling out this page) 5. Description of the invention (6) Contains no cyanide ions.
Na+，CN·之無機鹽水合物。 為含Ca++，Q-， 收率如下示 上述步驟以不同溶劑代替甲醇重複實驗， 實施例 溶劑（含水率） 上述步驟以不同陰離子代替Cl-重複實驗，Na +, CN · is an inorganic salt hydrate. It contains Ca ++ and Q-. The yield is shown below. The above steps were repeated with different solvents instead of methanol. Example Solvent (water content) The above steps were repeated with different anions instead of Cl-.
收率如下示 室溫下在10OmL反絲中放入甲醇(5〇 mL %)，氰化納（2.36 g，0.048莫耳)，氧化鐫（194&⑽:1·0 莫耳），攪拌一小時後陸續加入1-甲基吼啶氣盥(’6 8 0.048莫耳，）’触加熱至6〇±5。〇並轉科時^ 趁熱將甲醇溶液以氮氣加_過纽性_過 = 藍色不透鴨液於另-個反應瓶，將__ g 本緘張尺度逍用中國《家橾丰（CNS > A4规格（210:第1〇頁 經濟部中央橾準局员工消費合作社印製 393480 五、發明説明（ 醇後’冷卻至5至1〇。〇並維持一小時，過遽、乾燥得到藍 黑色結晶性粉末（即夂彳，-二曱基_44，_聯此啶鹽之前騍物） ’加入水（10ml)並在室溫下通入氣氣至内容物呈淡黃色， 其pH為4至6。得到1，*|，-二甲基·44，_聯吡啶氣鹽黃綠色油狀 溶液16g (UV定量Α.Ι.為35_0。/。），收率84%，分析内容物 中不含氰離子。 實施例八 室溫下在100 ml~反應瓶中放入甲醇(50mL，K.F.；=0.5 %)，氰化鈉（2.36 g, 0.482 莫耳)，氧化鋇(7.40g，0.048 莫耳）’授拌一小時後陸續加入1·甲基此啶氣鹽(62g， 0Ό48莫耳），過程加熱至6〇d^〇c並維持兩小時，内容 物趁熱將甲醇溶液以氮氣加壓經過多孔性濾頭過濾，收集 深藍色不透明濾液於另一個反應瓶，經減壓蒸餾回收甲醇 後，冷卻至5至1〇。&並維持一小時，過濾、乾燥得到藍黑 色結晶性粉末（即二曱基聯吡啶鹽之前驅物），加入 水（10ml)並在室溫下通入氣氣至内容物呈淡黃色，其pH為 4至6。得到1,1’_二甲基_4,4’_聯吡啶氣鹽黃綠色油狀溶液16 g (UV定量A.I.為31.0%)，收率81%，分析内容物中不含 氰離子。 本紙張尺反通用宁國國家橾準（) A4规格（210第H頁 ----------裝— (锖先閲讀背面之注$項再填寫本頁) ，Tr 線The yield is shown below. Methanol (50 mL%), sodium cyanide (2.36 g, 0.048 mol), osmium oxide (194 & ⑽: 1.0 mol) were placed in 100 mL transfilament at room temperature and stirred for one hour. After that, 1-methyl-pyridine gas was added successively ('6 8 0.048 mol,)' and heated to 60 ± 5. 〇 When transferring, ^ Add the methanol solution with nitrogen while it is still hot _ Pass button _ Pass = Blue impervious duck liquid in another reaction bottle, apply __ g of this standard to Chinese CNS > A4 specifications (210: page 10 printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 393480 V. Description of the invention (after the alcohol is cooled down to 5 to 100.0) and maintained for one hour. Blue-black crystalline powder (i.e., pyrene, -difluorenyl _44, _ linked to this pyridinium salt) 'Add water (10ml) and aerate at room temperature until the content is pale yellow, its pH It is 4 to 6. 16 g of 1, * |, -dimethyl · 44, _bipyridine gas salt yellow-green oily solution is obtained (UV quantitative A.I. is 35_0.%), The yield is 84%, and the analysis content No cyanide ions are contained in the sample. Example 8 Methanol (50 mL, KF; = 0.5%), sodium cyanide (2.36 g, 0.482 mol), and barium oxide (7.40 g) were placed in a 100 ml ~ reaction bottle at room temperature. , 0.048 mole) 'After 1 hour of mixing, 1 · methyl this pyridinium salt (62g, 0Ό48 mole) was added successively, the process was heated to 60 d ^ 〇c and maintained for two hours, the content was heated while the methanol solution Add nitrogen Filter through a porous filter and collect the dark blue opaque filtrate in another reaction bottle. After recovering the methanol by distillation under reduced pressure, cool to 5 to 10. Keep it for one hour, filter and dry to obtain a blue-black crystalline powder. (That is, the precursor of dipyridyl bipyridine salt), add water (10 ml) and aerate at room temperature until the content is pale yellow, and the pH is 4 to 6. 1,1'-dimethyl is obtained _4,4'_Bipyridine gas salt yellow-green oily solution 16 g (31.0% UV quantitative AI), yield 81%, analysis content does not contain cyanide ions. This paper rule is against Ningguo National Standard () A4 specifications (210, page H ---------- equipment-(锖 read the note $ on the back before filling this page), Tr line