419451 A7 經濟部中央標率局員工消費合作社印製 B7五、發明説明（1 ) 發明背最 芳香族異氰酸塩類（Aroaatic Isocyanate)是工業上 製造胺基甲酸_類衍生物（Carba^te)和生產聚胺基甲酸 酯（Polyurethane)化合物所需之原枓。前者是製造農藥殺 蟲劑及除草劑之原枓 > 多半來自單官能基結構之單異氰酸 塩（roonoisocyanate)衍生物，後者則來自雙官能基结構之 二異氰酸塩（diisocyanate)衍生物如甲苯二異氰酸塩（ To丨uenc Dijsocyanate, TDI)及亞甲基二苯基二異氰酸塩 (Methylene Diphenyldiisocyanate, MDI)等•其用途遍 及吾人日常生活之必需品包括硬質發泪、軟質發泡、彈性 體、塗料、合成皮等應用。異氰酸塩類早於1884年即由 Hentschel發現可由光氣和胺類反應而成，時至今日已有 270棰Μ上之異鎮酸塩類化合物被發現·但僅有MIH，TDI 及HDI [六亞甲基二異氰酸塩（Hexamethylene Diisocyanate)]等少數具工業上之應用價值。目前工業上 製造異氰酸塩類或胺基甲酸酯類化合物皆使用光氣法，除 了製備上有高度的危險性外•所產生的副產物塩酸亦會造 成嚴重的腐蝕和污染，因此開發非光氣法之二異氟酸塩製 程具有很高的潛在價值。 而二（烷氧羰胺基芳基）甲烷則係二異氰酸塩Μ非光氣 法製程中之中間物，其可經加熱分解而生成二異氰酸塩= 最早利用酸觸媒维行胺基甲酸醮類縮合反應之文獻於 1960年由KUuke等人揭露（美國專利USP 2946768)。該文 獻係Μ塩酸為觸媒進行胺基甲酸酷之縮合反應*且甲醛易 (請先聞讀背面之注意事項再填寫本頁) 装. 、1Τ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 3 1 5 4 5 6 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（2 ) 與胺基甲酸酯類上N-官能基反應生成N -笨甲基化合物。這 類化合物在進行加熱分解產生二異氰酸塩時不但不會生成 所需之異氰酸塩類|且對反應之產率、選擇率有不良之影 簪。且在反應之後尚須經遇一次重組反應，Μ減少其生成 (歐洲專利ΕΡ 0110732 Α2，美國専利USP 4146727)。頬Μ 结果亦出規於Μ磙酸作為觸媒之製程中（美國專利US Ρ 45 52974卜之後有闞胺基甲酸酗類之縮合反應專利尚包括 :固艚酸作為觴媒（歐洲專利EP 0027330A，EP 264744)， 路易士酸作為觸媒（歐洲專利EP 410684A2，美！8專利USP 5206412* 4307029，中華民國專利】6993?)，HP酸作為觸 媒（歐洲專利EP 406129，EP 410900·美國專利USP 5066827)及碕酸作為觸媒（美國專利USP 4552974，日本專 Μ JP 01211558 · JP 63150255， JP 01113358 * JP 0 1 1 3 5 7 5 8 - J P 0 2 1 0 8 6 5 8 )等。在固體酸反應方面，使用酸 性觴媒如Ambelyst 15成Ambelyst 36、超強酸類之金鼷氧 化物（如Zr〇2， Ti〇2, Ga2〇3等）分佈在氧化鋁或氧化矽之 擔體上Μ反酸性黏土、雑多酸（heteropoly acid)及沸石 等方面等亦可逹胺基甲酸酯縮合反應之效果。使用固體酸 觴媒固然有易於分離之優點，但是随著反應的_行，部份 S〇3H基會自樹脂上流失，或是活性基（active sites)遣毒 化導致觸媒失活，因此在觸媒再生方面必須適度加Μ酸化 Μ恢復其活性，在成本上似缺乏商業化利基。 在路易士酸及HP酸之觸媒方面報導相對較少•由於觸 媒的使用虽仍然很高，如就實際商業觀點而言*對製程分 -------Λ 裝------訂 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4現格（210Χ29?公釐） 4 1 5456 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明（3 ) 離有不利之影響，顯示觸媒活性仍有待改進。 磙酸作為觸媒方面的研究相對較多，在不同的澹度、 溶劑及使用方式上有不同的專利報導。其主要特點為：< 1)觸媒皆溶在水溶液糸統下進行縮合反應，其濃度自50 %至8〇%不等。（2)觭媒的使用量很大•硫酸/胺基甲酸 酯比例約在3 0 0〜5 0 0 0 w t % Μ上。（3 )觸媒是Μ溶劑或共溶 劑方式存在糸統中進行縮合反應*對製程分離技術較不利 C· 本發明人基於上述各製程之缺點加Κ研究•因而發現 利用濃碕酸作為觸媒在非水溶液糸下進行縮合反應f可改 良前述製程之缺點，因而完成本發明。 發朗目的 本發明之目的係提供一種二（烷氧羰胺基芳基）甲烷之 新穎製法。 馘眼註钿說明 本發明係提供一種具下列通式（I >之二（烷氧羰胺基 芳基）甲烷之新穎製法： Ri00CHH-Ari-CH2-Ar2-NHC00R2 I I ) 其中Rt及R2可相同或不同且分別表示（；卜6烷基，C2-6 烯基或C4-6烷二烯基*及An ^Ar2可相同或不同且分別 表示未取代之伸苯基或可經選自鹵素、Cl-3烷基、胺基、 C ! - 3烷氧基或羥基之収代基所取代之伸笨基； 該製法包括使下式U)及/或（m)所示之N-芳基胺基 甲酸醮： I-------裝------訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210XM7公釐） 5 1 5 4 5 6 經濟部中央標準局員工消費合作社印製 41945 1 A7 B7 五、發明説明（4 ) 8iOOCHH-Ari-H (Π ) R2OOCHN-ΑΓ2-Η (i ) (式中Ri、R2、Ari及Ar2均如上述定義）； 與甲醛類化合物在以澹醃酸作為酸性觸媒下進行縮合 依據本發明之新顆製法，僅需利用極少量之濃磺酸作 為觸媒，即可進行Ν -芳基胺基甲酸_之_合反應，並可以 高選擇率製得二（烷氧羰胺基芳基）甲烷。且由於觸媒用量 槿少，價格便宜無需回收，故製程之分離及_酸處理問題 得以簡化。再者》由於濃硫酸用量極少•無磺酸化反應發 生亦不會生成具有亞甲基-胺基鐽之類的副產物如Η-笨甲 基化合物（例如 C6HsH(C00CH3)(CH2CeH5NHC00CH3) ·因此 省略了習知Μ碕酸或塩酸作為觸媒之製程中霜再進行重組 反應之步驟。 本發明通式（I )中，Ri及R2所示之Cl-6烷基可為直_ 或支鐽烷基*包含例如甲基，乙基，正丙基，異丙基，正 丁基*異丁基，正戊基，異戊基，正己基，異己基等。其 中MCt-3烷基較佳，更好為甲基或乙基。 通式（Ϊ )中，fi t及R. 2所示之C 2 - 6烯基包含例如乙烯基 ，1-丙烯基，2 -丙烯基，1-丁烯基，2 -丁烯基，3 -丁烯基 ，1 -戊烯基，2 -戊烯基* 3 -戊烯基，4 -戊烯基，1 -己烯基 ，2 -己烯基，3 -己烯基，I己烯基* 5 -己烯基等。 通式（I )中，Rl及（Ϊ2所示之C4-6烷二烯基包含例如丁 二烯基，戊二烯基，己二烯基等。 I I,…装 I 訂 . (請先聞讀背面之注意事項再填寫本頁} 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1 5 4 5 6 41945 A7 經濟部中央標丰局員工消費合作社印製 B7五、發明説明（5 ) 通式（I )中，作為Αγμ及Ar^所示之伸苯基上之取代基 之鹵素包含例如氟、氣、溴、碘。 作為A「1及ΑΓ2所示之伸笨基上之取代基之燒基包 含例如甲基•乙基，正丙基，異丙基等。 作為Ari及（\「2所示之伸苯基上之取代基之Ci-3烷氣基 包含例如甲氧基t乙氧基，正丙氧基，異丙氧基等。 本發明之方法由於係在非水溶液糸統中進行反應，且 僅需相對於習知技術較少之濃硫酸量，因而無磺酸化反應 產生亦不會形成亞甲基-胺基键結之副產物，故省略了習 知碲酸及塩酸製程中所需Z重組反應步驟*使得製程更精 簡。 本發明方法中，作為起始物之甲醛類化合物為可提供 甲醛來源之衍生物*且可Μ氣態、固態或液態參與反應， 洌如甲醛氣體，福馬林，三氧雜擐己烷Urioxane)、多聚 甲醒（parafornaldehyde)等。 本發明方法中，式（Π )及/或（11)之|{-芳基胺基甲酸 酯與甲醛之反應莫耳比並無限制，但較好莫耳比在2-10之 間。 濃硫酸之濃度自妁9 5 %至1 00 % 之間，其用量相對於 芳基胺基甲酸_重虽為〇.]至，較好為0.1至l(>wt% 。濃硫酸之用量若低於O.lwt% 則導致反應不完全，若高 於S 0 w t % *除了增加製程成本外，亦會產生副產物。 本發明方法所用有機溶劑之種頬及用量並無限制，但 一般溶劑用量約佔反應總量之0〜95wt% ，而溶劑可為例 (請先閲讀背面之注意事項再填寫本頁) 衣· '訂 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） 7 1 5 456 A7 經濟部中央標隼局員工消費合作社印製 "n f f 々 B7五、發明説明（6 ) 如C5-20脂族，Cs-2〇環脂族，直_或支鐽烷烴·芳香族 或其他含有極性官能基之溶劑或其混合物，例如酵類，乙 酸乙醋，甲苯，二氣笨，二甲基甲_胺（0科}〇，四氫 呋喃（THP)，二甲亞《l(DHSO)或其混合物等。 本發明方法中之反應溫度在4 0至1 6 0 T之間，較好在 70至120C之間*反應壓力在0至lOks/cn2之間，反應時 間自0 . 2 5小時至數小時之間，視其他反應條件如溫度、壓 力、濃度、濃硫酸用量及溶劑種類及量而定，通常愫介於 0 . 2 5至5小時之間。 本發明將Μ下實胞例進一步加Μ說明，惟此等實施例 僅做為說明之用，並不限制本發明之範圍。以下所示之實 拖例中*有關反應之轉化率、選擇率及產率定義如下： 隨甲_之澥疆 隨甲画關之帱(碑：-xi_ 胺基甲 4,4，-二芳基)甲院莫* 4,4’-二芳基)-Xl〇〇^ 臓甲之鶸量(莫TO/2 2,4'-二基)甲院过JiM(期動 2,4 ·-二芳基)甲燒之-X100% 麵甲之消韻ΜϋΟ/2 聚-二甲烧量(箅_t) 聚-二芳基)甲烧之截-X100¾ 讎甲之麵量(》W/2 基芳基)甲烧漢耳數· 4,41-+2,(-+聚-} (^(»基芳基)甲»^率=-X 1〇〇 % 甲醒量(ίΜ) (請先閱讀背面之注意事項再填寫本頁) 裝- ，丁 -a 本紙張尺度適用中國國家梯準（CNS )八4規格（210'乂297公釐） 8 15456419451 A7 Printed B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (1) The most aromatic Aroaatic Isocyanate is the industrially produced carba ^ te derivative. And the raw materials required for the production of polyurethane compounds. The former is the original 枓 for the manufacture of pesticide insecticides and herbicides. Most of them are derived from monofunctional isoronium isocyanate derivatives, and the latter are derived from the difunctional diisocyanate derivatives. Toluene diisocyanate (TDI) and Methylene Diphenyldiisocyanate (MDI), etc. • Necessities that are used throughout our daily lives include hard tears, softness Foam, elastomer, coating, synthetic leather and other applications. Isocyanates were discovered by Hentschel as a reaction between phosgene and amines as early as 1884. Today, 270 镇 M isoisocyanates have been discovered. But only MIH, TDI and HDI [六Hexamethylene Diisocyanate] and a few other industrial applications. At present, the phosgene method is used in the industrial production of fluorene isocyanate or urethane compounds. In addition to the high degree of danger in preparation, the by-product osmic acid produced can also cause severe corrosion and pollution, so the development of non-photochemical Gas disulfonium isofluoride process has high potential value. Di (alkoxycarbonylaminoaryl) methane is an intermediate in the process of the non-phosgene method of diisocyanate, which can be decomposed by heating to form diisocyanate. The earliest use of acid catalysts The literature on ammonium carbamate condensation reactions was disclosed by KUuke et al. In 1960 (US Patent No. 2946768). This document is a catalyst for the condensation reaction of amino formic acid * and the formaldehyde is easy (please read the precautions on the back before filling out this page). 1T This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 3 1 5 4 5 6 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Reaction with N-functional groups on urethanes to form N-benzyl methyl compounds. When these compounds are thermally decomposed to produce europium diisocyanate, not only will they not produce the required europium isocyanate | but also have a negative effect on the reaction yield and selectivity. After the reaction, a recombination reaction has to be performed to reduce its production (European patent EP 0110732 Α2, US Patent USP 4146727). The results of MU are also formulated in the process of MU acid as a catalyst (U.S. Pat. No. 45 52974) and the condensation reaction of carbamic acid is also included. The patent also includes: sulfonic acid as a catalyst (European patent EP 0027330A , EP 264744), Lewis acid as catalyst (European patent EP 410684A2, US! 8 patent USP 5206412 * 4307029, Republic of China patent] 6993?), HP acid as catalyst (European patent EP 406129, EP 410900 · US patent USP 5066827) and osmic acid as catalysts (U.S. patent USP 4552974, Japanese patent JP 01211558 · JP 63150255, JP 01113358 * JP 0 1 1 3 5 7 5 8-JP 0 2 1 0 8 6 5 8) and so on. In terms of solid acid reaction, acidic media such as Ambelyst 15 to Ambelyst 36, and super strong acid gold oxides (such as ZrO2, TiO2, Ga2O3, etc.) are distributed on the support of alumina or silica. The anti-acid clay, heteropoly acid, zeolite, etc. can also have the effect of the urethane condensation reaction. The use of a solid acid catalyst has the advantage of easy separation, but with the reaction of Parts of the SO3H group will be lost from the resin, or It is because active sites are poisoned and the catalyst is inactivated. Therefore, in the regeneration of the catalyst, it must be moderately added to acidify the M to restore its activity, and it seems that it lacks a commercial niche in cost. There are relatively few reports in the media. • Although the use of catalysts is still very high, as far as the actual business point of view is concerned, * the process is divided into --- Λ installation --- order (please read the back of the first Note: Please fill in this page again.) This paper size applies Chinese National Standard (CNS). A4 is now standard (210 × 29? Mm). 4 1 5456 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the invention (3) The adverse effect shows that the catalytic activity still needs to be improved. There are relatively many studies on osmic acid as a catalyst, and there are different patent reports on different degrees, solvents and use methods. Its main characteristics are: < 1) The catalysts are all dissolved in the aqueous system to perform the condensation reaction, and the concentration ranges from 50% to 80%. (2) The amount of media used is very large. The ratio of sulfuric acid / urethane is about 300 ~ 5000 w t% Μ. (3) The catalyst is M solvent or co-solvent. The condensation reaction exists in the system. * It is not good for the process separation technology. C. The inventor based on the shortcomings of the above processes plus K research. Therefore, it was found that concentrated acetic acid was used as the catalyst. Performing the condensation reaction f in a non-aqueous solution can improve the disadvantages of the foregoing processes, and thus the present invention has been completed. The purpose of the present invention is to provide a novel method for producing bis (alkoxycarbonylaminoaryl) methane. (Eye note) The present invention provides a novel method for preparing methane (alkoxycarbonylaminoaryl) methane having the following general formula (I > bis (alkoxycarbonylaminoaryl) methane: Ri00CHH-Ari-CH2-Ar2-NHC00R2 II) where Rt and R2 may be The same or different and respectively represent (; 6 alkyl, C2-6 alkenyl or C4-6 alkadienyl * and An ^ Ar2 may be the same or different and respectively represent unsubstituted phenylene or may be selected from halogen , Cl-3 alkyl, amine, C! -3 alkoxy or hydroxyl substituted substituents; the production method includes making N-aryl represented by the following formula U) and / or (m) Urethane: I ------- Packing ------ Order (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210XM7) 5) 5 1 5 4 5 6 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 41945 1 A7 B7 V. Invention Description (4) 8iOOCHH-Ari-H (Π) R2OOCHN-ΑΓ2-Η (i) (where Ri, R2, Ari, and Ar2 are as defined above); condensation with formaldehyde compounds using arsenic acid as the acidic catalyst according to the new method of the present invention, only a small amount of concentrated sulfonic acid is required as the catalyst, That is, the reaction of N-arylaminocarboxylic acid can be performed, and bis (alkoxycarbonylaminoaryl) methane can be obtained with high selectivity. And because the amount of catalyst is small, the price is cheap and no recycling is needed, so the problem of separation of the process and acid treatment can be simplified. Furthermore, “Since the amount of concentrated sulfuric acid is very small. • No sulfonation reaction will occur, and no by-products such as methylene-benzyl methyl compounds (such as C6HsH (C00CH3) (CH2CeH5NHC00CH3)) will be generated. The conventional step of reconstituting the frost in the process of hydrazine or acetic acid as a catalyst is described. In the general formula (I) of the present invention, the Cl-6 alkyl group represented by Ri and R2 may be straight or branched The group * includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl * isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, etc. Among them, MCt-3 alkyl is preferred, More preferably, it is methyl or ethyl. In the general formula (VII), the C 2-6 alkenyl represented by fi t and R. 2 includes, for example, vinyl, 1-propenyl, 2-propenyl, and 1-butene. , 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl * 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, Ihexenyl * 5-hexenyl, etc. In the general formula (I), C4-6 alkyldienyl represented by R1 and (2) includes, for example, butadienyl, pentadienyl , Hexadienyl, etc. II, ... I order. (Please read the back Please fill in this page again for the matters needing attention} This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1 5 4 5 6 41945 A7 Printed by the Consumer Standards Cooperative of Biaofeng Bureau, Ministry of Economic Affairs, B7 V. Invention Description (5) In the general formula (I), the halogen as the substituent on the phenylene group represented by Aγμ and Ar ^ includes, for example, fluorine, gas, bromine, and iodine. As the substituent on the phenylene group represented by A1 and AΓ2, The alkyl group includes, for example, methyl ethyl, n-propyl, isopropyl, etc. Ci-3 alkyl groups which are substituents on the phenyl group shown in Ari and (2) include, for example, methoxy t Ethoxy, n-propoxy, isopropoxy, etc. Since the method of the present invention is carried out in a non-aqueous system, and only requires a relatively small amount of concentrated sulfuric acid compared to conventional techniques, there is no sulfonation reaction Produces by-products that do not form a methylene-amine bond, so the conventional Z recombination reaction step * required in the conventional telluric acid and osmic acid processes is omitted to make the process more streamlined. In the method of the present invention, it is used as a starting material. Formaldehyde compounds are derivatives that provide a source of formaldehyde * and can be used in gaseous, solid or liquid form Participate in the reaction, such as formaldehyde gas, formalin, trioxane (Urioxane), parafornaldehyde, etc. In the method of the present invention, the {{-aryl group of formula (Π) and / or (11) The molar ratio of urethane to formaldehyde is not limited, but the molar ratio is preferably between 2 and 10. The concentration of concentrated sulfuric acid ranges from 95% to 100%. Although the weight of aminocarbamic acid is from 0.1% to, preferably from 0.1 to 1 (> wt%). If the amount of concentrated sulfuric acid is less than 0.1 wt%, the reaction will be incomplete, and if it is higher than S 0 w t% * In addition to increasing process costs, by-products will also be generated. There are no restrictions on the amount and amount of organic solvents used in the method of the present invention, but the general amount of solvent is about 0 to 95% by weight of the total reaction, and the solvent can be taken as an example (please read the precautions on the back before filling this page). 'The size of the paper is in accordance with the Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 7 1 5 456 A7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs " nff 々B7 V. Description of the invention (6) C5-20 aliphatic, Cs-20 cycloaliphatic, straight or branched alkane · aromatic or other solvents or mixtures containing polar functional groups, such as yeasts, ethyl acetate, toluene, dioxin, two Methylmethylamine (0 Branch) 0, tetrahydrofuran (THP), dimethylene (1 (DHSO) or a mixture thereof, etc.) The reaction temperature in the method of the present invention is between 40 and 160 T, preferably between Between 70 and 120C * Reaction pressure is between 0 and 10Ks / cn2, and reaction time is from 0.25 hours to several hours, depending on other reaction conditions such as temperature, pressure, concentration, amount of concentrated sulfuric acid, and type and amount of solvent However, it usually ranges from 0.2 to 5 to 5 hours. Step-by-step instructions are provided, but these examples are for illustrative purposes only and do not limit the scope of the present invention. In the practical examples shown below *, the conversion, selectivity and yield of the reaction are defined as follows: _ 之 澥 jiang Sui Jia Hua Guan Zhi (Stone: -xi_ Aminomethyl 4,4, -diaryl) Jiayuan Mo * 4,4'-diaryl) -Xl〇〇 ^ (Mo TO / 2 2,4'-diyl) Jiayuan over JiM (periodically active 2,4 · -diaryl) -X100% of the scent of facial nail ΜϋΟ / 2 poly-dimethylformate (箅 _t) poly-diaryl) terephthalate-X100¾ face of terephthalate (》 W / 2 arylaryl) number of terephthalate · 4,41- + 2, (-+ poly-) ( ^ (»基 芳 基) 甲» ^ Rate = -X 100% Amount of Awake (ίΜ) (Please read the notes on the back before filling out this page) Pack-， 丁 -a This paper size is applicable to the Chinese national ladder Standard (CNS) 8 4 specifications (210 '乂 297 mm) 8 15456
經濟部中央標隼局員工消费合作社印I Α \9^5 Λ Α7 Β7五、發明説明（7 ) 在Μ下所揭示實例中，縮合反應是在1升之三頸瓶内 進行。溫度控制由熱電偶（them丨coupie)插人反應溶液 之中Μ控制加熱器，加熱方式是由加熱包控制。反應後固 體產物經過濾後Μ適量之氰甲烷溶解後可Μ管柱色層分析 法tColuan Chronatography)將其純化並分維之。產物分 析亦可用高效眭液相層析儀（HPLC)分析之> HPLC使用 Waters 600E，管柱使用 Merck tLiL'hroL'ARTSupei'sptier 100 RP-18 ODS 4.6x 250nm規格，可得產物分離之效果， UV偵測器（Waters型號490)波長設在254nra ·溶劑流逮為 leL/mirt。所分離纯化後的產物結構是經由lMPerkin Ε 1 Her FT 18 System 2000， KBr) · k N H R ( V a r i a n 2 0 0 HHz spectroBeter，使用 de-DMSO， （;DC]3/TMS為參考峰）等儀 器鑑定。 當撫例1及hh齩例1〜3 本實SS例1及比較例1〜3係利用各種酸觴媒（濃硫酸、 固體酸、液體酸、路易士酸）在相同之反應條件下進行N-芳基胺基甲酸®類之縮合反應，並比較反應结果ΰ其實施 方法如下：在1L之玻璃容器内置人100克（0.6莫耳％ )的Ν-笨基胺基甲酸乙贿（Ethyl H-phenylcarbamate) 、 0.12 輿 耳的甲醛（35%水溶液）、250πΗ 之甲苯、及不同濃度的各 種酸觸媒。所有反應物均在同一時間加入後*反應在90 t ，1大氣壓下進行]小時後Μ Η P L【:測試其反應结果，結果如 下： (請先閱讀背面之注意事項再填寫本頁) 策· ,1Τ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 9 1 5 4 5 6 五、發明説明（ A7 B7 經濟部中央標準局員工消費合作社印裝 實施例1 比較例3 比較例2 比較例ΐ 實例編號 98¾ H2SO4 1 ZnCl2 1 1 Ambertyst- 15 i 60¾ H2SO4+ i CFsCOOH I ... 觸媒種類 ΓΟ ϊί 100 ! 300-5000 丨 1 爾濾澱 ί \进 t m m 1 it -a 办 cn 0 ro CO OS 轉化率 1 1 fO «η σϊ LC 2,r-產物 遘擇率（¾) σ> <x 0 ¢0 OC 4f4f-產物 μ-α s CJi to 聚-產物 ΓΟ m m 逾漉 w » m $ ?3Ι〆 爾 。 姍 C Γνί *—* m m 蔴m m m 陬莰 备薄 忒 Μ 薄 。 〇 fO m m m m 制瞄 诤薄 湘m Μ 。 商 ο ro — ^ k h m 愍趣 S91兴 m _ 。 沖 ο 備註 -------- 装------訂 0 r ' (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 1 5 456 编 10. Iff 五、發明說明（9 ) w m俐2 (請先《讀背面之注意事項再填寫本頁) 在1L之玻瑰容器内置入100克（0.6莫耳）的H-苯基胺基 甲酸乙 _ (Ethyl N-phenylca「bamate) 、 0.12 莫耳的三氧 雜環己烷（trioxane)、250bL之甲苯及0.25克的98¾準磙 酸。所有反應物均在同一時間加入後*反應在90Ό，1大 氣壓下進行1小時後MHPLC測試其反應结果，其中Η -苯基 氨基甲酸乙酯之轉化率為42¾ ，4,4’ -二（乙氧羰胺基苯基 )甲烷之選擇率為61¾ ，2,4’-二（乙氧羰胺基苯基）甲烷之 選擇率為28¾ ，三聚體（聚-產物）之埋擇率為11¾ ，（乙氧 羰胺基苯基）甲烷類之產率為92 % 。反應混合物纆潮試 分析後顯示主要成份為N-苯基胺基甲酸乙醱（殘餘之反應 起始物）及二（乙氧羰胺基苯基）甲烷，幾乎不含N,C’-縮合 反應之異構物（CeHsMCOOEt) (CH2C6H5NHC00Et)及確酸化 之類的產物}。因此不需再進行重組反應步驟。 在室溫下，於反應產物中添加250奄升0.025N NaOH並 攪拌10分鐘後，置靜分層，分離水相後，於有櫬層中添加 250奄升去離子水，再攪拌10分鏟，靜置分層*移除水相 後*有櫬相以批式蒸饉方式分離甲苯、N-苯基胺基甲酸乙 酯（54.5克*110'^*3|11111^)及二（乙氧羰胺基苯基）甲烷（ 37.7¾ ， 180， ΙημβΗκ) 〇 g濂钏3 經濟部智慧財產局員工消費合作社印製 在U之玻璃容器内置入100克（0.6萁耳）的N-苯基胺基 甲酸乙基酷、0.12賓耳的多聚甲薛（paraforaaldeyde)、 250bL之二氮苯、及0.25克的98¾濃硫酸。所有反ϋ物均 在同一時間加入後，反應在120它，1大氣懕下進行1小時 後以HPLC測試其反應结果：其中Ν-苯基胺基甲酸乙酯之轉 化率為43¾ ，4,4·-二（乙氧羰胺基苯基）甲烷之選擇率為 65« ，2,二（乙氧羰胺基苯基）甲烷之S擇率為25% · 三聚物（聚-產物）之選擇率為10¾ •(乙氧羰胺基笨基）甲 本紙張尺度適用中國國家標準（CNS)A4规格（210 X 297公釐） 11(修正頁>15456 419451 A7 B7 年月組10.Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs I Α \ 9 ^ 5 Λ Α7 B7 V. Description of the Invention (7) In the example disclosed under M, the condensation reaction is performed in a three-necked bottle of 1 liter. The temperature is controlled by a thermocouple (them coupie) inserted into the reaction solution. The heater is controlled by a heating pack. After the reaction, the solid product is filtered and the appropriate amount of cyanomethane is dissolved, and the solid product can be purified by fractal column chromatography (tColuan Chronatography). Product analysis can also be analyzed by high performance 眭 liquid chromatography (HPLC) > HPLC uses Waters 600E, the column uses Merck tLiL'hroL'ARTSupei'sptier 100 RP-18 ODS 4.6x 250nm specifications, the effect of product separation can be obtained The wavelength of UV detector (Waters model 490) was set at 254nra. The solvent flow was set to leL / mirt. The structure of the separated and purified product was passed through 1MPerkin Ε 1 Her FT 18 System 2000, KBr · k NHR (Varian 2 0 0 HHz spectroBeter, using de-DMSO, (; DC] 3 / TMS as the reference peak) and other instruments Appraisal: When the first and second examples of hh, examples 1 to 3, SS example 1 and comparative examples 1 to 3 are using various acid solvents (concentrated sulfuric acid, solid acid, liquid acid, Lewis acid) under the same reaction conditions The condensation reaction of N-arylaminocarboxylic acid® was performed, and the reaction results were compared. The implementation method is as follows: 100 grams (0.6 mole%) of N-benzylaminocarboxylic acid ethyl ester was built in a 1L glass container ( Ethyl H-phenylcarbamate), 0.12 M formaldehyde (35% aqueous solution), 250πΗ toluene, and various acid catalysts of different concentrations. All reactants are added at the same time. * The reaction is performed at 90 t at 1 atmosphere] Hours M Η PL [: Test the reaction results, the results are as follows: (Please read the precautions on the back before filling out this page) Policy ·, 1Τ This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 9 1 5 4 5 6 V. Description of the invention (A7 B7 Printed by the Ministry of Economic Affairs of the Central Bureau of Consumers Cooperative Example 1 Comparative Example 3 Comparative Example 2 Comparative Example ΐ Example number 98¾ H2SO4 1 ZnCl2 1 1 Ambertyst- 15 i 60¾ H2SO4 + i CFsCOOH I ... Catalyst type ΓΟ ϊί 100! 300 -5000 丨 1 ER filter lake \ tmm 1 it -a cn 0 ro CO OS conversion rate 1 1 fO «η σϊ LC 2, r-product selectivity (¾) σ > < x 0 ¢ 0 OC 4f4f-product μ-α s CJi to poly-product ΓΟ mm over 漉 w »m $? 3Ι〆 尔. Shan C Γνί * — * mm hemp mmm Preparation thin thin film. 〇fO mmmm Manufacture thin thin m Μ. 商 ο ro — ^ khm 愍 趣 S91 兴 m _. rush ο Remarks -------- equipment ---- order 0 r '(Please read the precautions on the back before filling in this (Page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1 5 456 Ed. 10. Iff V. Description of invention (9) wmLi 2 (please read the “Notes on the back side before filling this page”) Put 100 g (0.6 mol) of H-phenylaminocarbamate (Ethyl N-phenylca "bamate", 0.12 mol trioxane in a 1L glass container (Trioxane), 250bL of toluene, and 0.25 g of 98¾ pseudoacid. After all the reactants were added at the same time, the reaction was carried out at 90 Torr and 1 atmosphere for 1 hour. The MHPLC test results showed that the conversion of hydrazone-phenylcarbamate was 42¾, 4,4'-bis (ethyl The selectivity of oxycarbonylaminophenyl) methane is 61¾, the selectivity of 2,4'-bis (ethoxycarbonylaminophenyl) methane is 28¾, and the selectivity of trimer (poly-product) is 11¾ The yield of (ethoxycarbonylaminophenyl) methanes was 92%. The analysis of the reaction mixture showed that the main components were N-phenylaminoacetic acid acetamidine (residual reaction starter) and bis (ethoxycarbonylaminophenyl) methane, which contained almost no N, C'-condensation. The reaction isomers (CeHsMCOOEt) (CH2C6H5NHC00Et) and products like acidification}. Therefore, no recombination step is required. At room temperature, 250 liters of 0.025N NaOH was added to the reaction product and stirred for 10 minutes, and the layers were allowed to stand still. After the aqueous phase was separated, 250 liters of deionized water was added to the reaction layer and stirred for 10 minutes. , Standing and layering * after removing the water phase * there is a phase to separate toluene, N-phenylcarbamate (54.5 g * 110 '^ * 3 | 11111 ^) and di (ethyl Oxycarbonylaminophenyl) methane (37.7¾, 180, ΙημβΗκ) 〇g 濂 钏 3 Printed in the U.S. Intellectual Property Bureau Employees' Cooperatives in a glass container with 100 grams (0.6 萁) of N-phenyl Ethyl aminocarbamate, 0.12 bins of paraforaaldeyde, 250 bL of diazabenzene, and 0.25 g of 98¾ concentrated sulfuric acid. After all the reactants were added at the same time, the reaction was performed at 120 ° C, and the reaction was performed by HPLC after 1 hour under atmospheric pressure. The reaction result was determined by HPLC: the conversion of N-phenylcarbamate was 43¾, 4,4 · -Di (ethoxycarbonylaminophenyl) methane selectivity is 65 «, 2, Di (ethoxycarbonylamino) methane selectivity is 25% · Trimer (poly-product) The selection rate is 10¾ • (ethoxycarbonylbenzyl) A paper size applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 11 (correction page> 15456 419451 A7 B7 month group 10.
修正I 經濟部智慧財產局員工消t合作杜印製 五、發明說明（1 % 烷類之產率為90¾ 。反應混合物缕NMR測試分析埃顯示主 要成份為N-苯基胺基甲酸乙酯（殘餘之反應起始物）及二（ 乙氧羰胺基苯基）甲烷，嫌乎不含N,C’-縮合反應之異構物 (06HsN(C00Et) (CH2C6H5NHC00Et)及碌酸化之類的產物）。 因此不爾再進行重組反應步味。 在室溫下，於反應產物中添加250奄升0.025N HaOH並 攪拌10分鐘後，置靜分層，分離水相後•於有機層中添加 250毫升去離子水*再携拌10分鐘，靜置分層，移除水相 後•有襪相以批式蒸覦方式分離二氛苯、H-苯基胺基甲酸 乙酯（50.2克· 1101C ，3nmHg)及二（乙氧羰胺基苯基）甲烷 (35¾ · 180¾ * lniiHg)0 窗淪例4 在1L之玻璃容器内置人100克（0.66莫耳）的N-苯基胺 基甲酸甲蠢（Methyl N-phenylca「bamate) 、 0.12莫耳的福 馬林、250mL之甲苯及0.5克的98¾濃碕酸。所有反應物均 在同一時間加入後，反應在90它* 1大氣懕下進行3小時後 MHPLC測試其反應结果，其中N -苯基胺基甲酸甲ϋ之轉化 率為39% ·4,4’-二（甲氧羰胺基苯基）甲烷之選擇率為78 % ，2,4’-二（甲氧羰胺基苯基）甲烷之選揮率為19¾ ，三 聚物（聚-產物）之選擇率為3¾ ，（甲氧羰胺基苯基）甲烷類 之產率為93% 。反應混合物經ΝΜί{測試分析後顯示主要成 份為苯基胺基甲酸甲酯（殘餘之反應起始物）及二（甲氧 羰胺基苯基）甲烷，幾乎不含N,C’-縮合反應之異構物（（ CsHsNKOOMe) (CLCsHsNHCOOMe)及攝酸化之類的產物）。 因此不需再進行重組反應步驟。 在室溫下•於反應產物中添加500奄升0.025N HaOH並 攪拌10分鐘後，置靜分層，分離水相後*於有櫬層中添加 250毫升去離子水，再攪拌10分鐘，靜置分層，移除水相 後|有櫬相以批式蒸皤方式分皤甲苯、M-苯基胺基甲酸甲 本纸張尺度適用中國0家標準（CNS)A4規格<210 X 297公釐） 12 (修正頁）1 5 45 6 ------;------& • n n n tt t— i n If 1 n n I <請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局I工消费合作杜印製 4 19451 A7 寻月— . B7 89.10. 13 五、發明說明（η ) _(53.1克* UOt： · 3bh[U)及二（甲氧羰胺基苯基）甲烷（ 35 克· 1801，lmHg) v m m ^ 在1L之玻璃容器内置入100克（0.66莫耳）的N-苯基胺 基甲酸甲_、0.12萁耳的甲醛氣、250bL之二氛苯、及0.5 克的98¾瀠疏酸。所有反應物均在同一時間加入後，反應 在120t | 1大氣壓下進行2小時後MHPLC涵試其反應结果 *其中N -苯基胺基甲酸甲酯之轉化率為21¾ ，4,4匕二（甲 氧羰胺基苯基）甲烷之選擇率為89¾ ，2,4〜二（甲氧羰胺 基苯基）甲烷之S擇率為0% *三聚物（聚-產物）之遘擇率 為11¾ ，（甲氧捩胺基苯基）甲烷類之產率為90¾ 。反應混 合物經HMR測試分析後顯示主要成份為苯基胺基甲酸甲 _(殘餘之反應起始物）及二（甲氧羰胺基苯基）甲烷|幾乎 不含N,C'-嫌合反應之異構物（（CsHsN(C00Me)(CH2C6H5 HHCOOHe)及磺酸化之類的產物）。因此不需再進行重組反 應步驟。 在室溫下•於反應產物中添加500奄升0.025N NaOH並 攪拌10分鐘後•置靜分靥，分離水相後，於有機靥中添加 250奄升去雄子水 > 再攪拌10分鐘•靜置分層，移除水栢 後，有櫬相以批式蒸餹方式分離甲苯、N-苯基胺基甲酸甲 酯（73.1克，110T > 3amHg)及二（甲氧羰胺基苯基）甲烷（ 19. 6 克· 180 t，lnaiHg 卜 資施例6 在1L之玻璃容器内置入100克（0.6萁耳）的N-苯基胺基 甲酸乙酯、0.12其耳的甲醛（35¾水溶液）、及0.25克的98 %濃磙酸。所有反應物均在同一時間加入後，反應在30nL 的忖，1-二甲基甲醢胺（0从？）80它，1大氣壓下進行3小時後 MHPLC測試其反應结果：其中N -苯基胺基甲酸乙_之轉化 率為43% * 4, 4'-二（乙氧羰胺基苯基）甲烷之埋擇率為65 本紙張尺度適^令國國家標準（CNS)A4規格（210 * 297公釐) 13(修正頁)1 5 4 5 6 lit — —— — — — — ! 裝·—----訂·! I.竣 (請先《讀背面之注意事項再填寫本頁) 419451 A7 B7Amendment I Cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs. Du Yinchu 5. Invention description (1% alkanes yield 90¾. The reaction mixture was analyzed by NMR test and showed that the main ingredient was N-phenylcarbamate ( Residual reaction starter) and bis (ethoxycarbonylphenyl) methane, isomers (06HsN (C00Et) (CH2C6H5NHC00Et) and N-C'-condensation reaction which do not contain N, C'-condensation reaction ). Therefore, the recombination reaction step is performed. At room temperature, add 250 奄 liters of 0.025N HaOH to the reaction product and stir for 10 minutes, then stand still and separate the aqueous phase. • Add 250 to the organic layer. Milliliter of deionized water * Stir for another 10 minutes, let stand and separate, and remove the aqueous phase. • There is a sock phase to separate dioxobenzene and H-phenylcarbamate (50.2 g · 1101C) by batch distillation. 3nmHg) and bis (ethoxycarbonylaminophenyl) methane (35¾ · 180¾ * lniiHg) 0 Window Example 4 A 100 g (0.66 mol) N-phenylaminocarbamate was built into a 1L glass container. Stupid (Methyl N-phenylca "bamate", 0.12 moles of formalin, 250 mL of toluene and 0.5 g of 98¾ concentrated acetic acid. After all the reactants were added at the same time, the reaction was carried out at 90 ° C * 1 for 3 hours, and the results were measured by MHPLC. The conversion rate of N-phenylaminoformamate was 39%. 4,4'- The selectivity of bis (methoxycarbonylaminophenyl) methane is 78%, the selectivity of 2,4'-bis (methoxycarbonylaminophenyl) methane is 19¾, and the selectivity of trimer (poly-product) The selectivity is 3¾, and the yield of (methoxycarbonylaminophenyl) methanes is 93%. After the reaction mixture is tested and analyzed, the main component is methylphenylaminoformate (residual reaction starting material) And bis (methoxycarbonylaminophenyl) methane, it is almost free of isomers of N, C'-condensation reaction ((CsHsNKOOMe) (CLCsHsNHCOOMe) and products such as acidification). Therefore, no recombination reaction is needed. At room temperature • Add 500 liters of 0.025N HaOH to the reaction product and stir for 10 minutes. Allow the layers to separate and separate the aqueous phase. * Add 250 ml of deionized water to the aqueous layer and stir for 10 minutes. , Standing still and layering, after removing the aqueous phase | Toluene phase was separated into toluene and M-phenylaminoformic acid by batch distillation This paper size applies to 0 Chinese standards (CNS) A4 specifications < 210 X 297 mm) 12 (correction page) 1 5 45 6 ------; ------ & • nnn tt t — In If 1 nn I < Please read the precautions on the back before filling out this page) Printed by I Industrial Consumption Cooperation, Intellectual Property Bureau, Ministry of Economic Affairs 4 19451 A7 Moon Search —. B7 89.10. 13 V. Description of Invention (η) _ (53.1 grams * UOt: · 3bh [U) and bis (methoxycarbonylaminophenyl) methane (35 grams · 1801, lmHg) vmm ^ 100 grams (0.66 moles) of N are built into a 1L glass container -Phenylaminocarbamate, 0.12 moles of formaldehyde gas, 250 bL of dibenzobenzene, and 0.5 g of 98¾ acetic acid. After all the reactants were added at the same time, the reaction was performed at 120t | 1 atmosphere for 2 hours. The results were determined by MHPLC. * Among them, the conversion rate of methyl N-phenylcarbamate was 21¾, 4,4. The selectivity of methoxycarbonylaminophenyl) methane is 89¾. The selectivity of S for 2,4 ~ bis (methoxycarbonylaminophenyl) methane is 0%. * The selectivity of trimer (poly-product) It is 11¾, and the yield of (methoxymethoxyaminophenyl) methane is 90¾. The HMR test analysis of the reaction mixture showed that the main components were methyl phenylcarbamate_ (residual reaction starter) and bis (methoxycarbonylaminophenyl) methane | almost no N, C'-synthetic reaction Isomers ((CsHsN (C00Me) (CH2C6H5 HHCOOHe) and sulfonated products). Therefore, no recombination step is required. At room temperature • 500 liters 0.025N NaOH is added to the reaction product and stirred After 10 minutes • Allow to stand and separate. After separating the water phase, add 250 liters of deionized water to the organic mash. Stir for another 10 minutes. Separation of toluene, methyl N-phenylaminocarbamate (73.1 g, 110T > 3amHg) and bis (methoxycarbonylaminophenyl) methane (19.6 g · 180 t, lnaiHg) in diluent mode. Example 6 A 1-liter glass container was filled with 100 g (0.6 萁) of N-phenylaminocarbamate, 0.12 aldehyde formaldehyde (35¾ aqueous solution), and 0.25 g of 98% concentrated acetic acid. All the reactants were in After the addition at the same time, the reaction was performed at 30 nL of fluorene, 1-dimethylformamide (0 from?) 80, and after 3 hours at 1 atmosphere MHPLC test results: the conversion rate of N-phenylaminocarbamate is 43% * 4, 4'-bis (ethoxycarbonylaminophenyl) methane burying rate is 65 Ordering country national standard (CNS) A4 specifications (210 * 297 mm) 13 (correction page) 1 5 4 5 6 lit — —— — — — —! "Read the precautions on the back before filling out this page) 419451 A7 B7
1 «ft IQ 經濟部智您財產局員工消費合作社印焚 五、發明說明（12) % ，2,4'-二（乙氧羰胺基苯基）甲烷之遘擇率為25% *三 聚物（聚-產物）之選擇率為10¾ | (乙氧羰胺基苯基）甲烷 類產率為90% 。反應混合物經HMR測試分析後顯示主要成 份為N-苯基胺基甲酸乙醮（殘餘之反應起始物）及二（乙氧 羰胺基苯基）甲烷，幾乎不含H,C’-縮合反應之異構物（ C6H5N(C00Et) (CH2C6H5NHC00Et)及磺酸化之類的產物）。 因此不需再進行重組反應步驟。 在室溫下•於反應產物中添加250毫升0.025N NaOH並 攪拌10分鐘後，置靜分層 > 分離水相後*於有機層中添加 250奄升去雛子水，再攪拌10分鐘•靜置分層，移除水相 後，有拥相以批式蒸餾方式分離甲苯、H -苯基胺基甲酸乙 賄（49.2克，110七，3|11!11^)及二（乙氧羰胺基苯基）甲烷（ 36. 9 克，180¾，lniHg) 〇 在U之玻璃容器内置人100克（0.66莫耳）的N-苯基胺 基甲酸甲_、0.12莫耳的甲醛（35¾水溶液）、及0.25克 的98 %濃硫酸。所有反懕物均在同一時間加入後，反應在 701，1大氣壓下進行2小時後KHPLC測試其反應结果：其 ，中Ν-苯基胺基甲酸甲SS之轉化率為19¾ * 4, 二（甲氧羰 胺基苯基）甲烷之選擇率為58% ，2,4’-二（甲氧羰胺基苯 基）甲烷之S擇率為27¾ *三聚物（聚-產物）之選擇率為 15¾ •(甲氧羰胺基苯基）甲烷類產率為80% 。反應混合 物經NMR測試分析後頚示主要成份為H-苯基胺基甲酸甲酯 (殘餘之反應起始物）及二（甲氧羰胺基苯基）甲烷·幾乎不 含 N,C'-縮合反應之異構物（C6HsH(C00Me) (CIUCeHsNHCOOMe )及磺酸化之類的產物）。因此不需再進行重驵反應步驟。 在室溫下•於反應產物中添加250牽升0.025N NaOH並 撹拌10分鐘後，置靜分層，分離水相後，於有櫬層中添加 250毫升去雛子水，再攪拌10分鐮*靜置分暦，移除水相 後，有機相Μ批式蒸豳方式分離甲苯、H -苯基胺基甲酸乙 酯（72克，110TC ，3naiHg)及二（乙氧羰胺基苯基）甲烷（ 30.1¾ - 180 t · lminHg) ° 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）1 «ft IQ Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12)%, the selectivity of 2,4'-bis (ethoxycarbonylaminophenyl) methane is 25% * trimerization The selectivity of the product (poly-product) is 10¾ | (ethoxycarbonylaminophenyl) methane yield is 90%. The HMR test analysis of the reaction mixture showed that the main components were N-phenylaminoacetic acid ethylammonium (residual reaction starter) and bis (ethoxycarbonylaminophenyl) methane, which contained almost no H, C'-condensation. Reaction isomers (C6H5N (C00Et) (CH2C6H5NHC00Et) and sulfonated products). Therefore, no recombination step is required. At room temperature • Add 250 ml of 0.025N NaOH to the reaction product and stir for 10 minutes, then stand still and separate the layers> After separating the aqueous phase * Add 250 liters of deionized water to the organic layer, and stir for another 10 minutes. After the layers were separated and the aqueous phase was removed, toluene and H-phenylaminocarbamate (49.2 g, 110, 3 | 11! 11 ^), and di (ethoxycarbonyl) were separated by a batch distillation method after the aqueous phase was removed. Aminophenyl) methane (36.9 grams, 180¾, lniHg) 〇 100 grams (0.66 moles) of N-phenylcarbamic acid methyl formaldehyde, 0.12 moles of formaldehyde (35¾ aqueous solution) were built in a U glass container ), And 0.25 grams of 98% concentrated sulfuric acid. After all the reactants were added at the same time, the reaction was performed at 701.1 atmosphere pressure for 2 hours and the KHPLC test showed the reaction result: its conversion rate of N-phenylaminoformic acid methyl SS was 19¾ * 4, two ( The selectivity of methoxycarbonylaminophenyl) methane is 58%, and the selectivity of S of 2,4'-bis (methoxycarbonylaminophenyl) methane is 27¾. * The selectivity of trimer (poly-product) The yield of 15¾ • (methoxycarbonylaminophenyl) methane is 80%. The NMR test analysis of the reaction mixture revealed that the main components were methyl H-phenylaminocarbamate (residual reaction initiator) and bis (methoxycarbonylaminophenyl) methane. It contained almost no N, C'- Isomers of condensation reactions (C6HsH (C00Me) (CIUCeHsNHCOOMe) and sulfonated products). Therefore, it is not necessary to carry out the re-liming reaction step. At room temperature • Add 250 liters of 0.025N NaOH to the reaction product and stir for 10 minutes, then stand still and separate the layers. After the aqueous phase is separated, add 250 ml of water to the broiler layer and stir for 10 minutes. * After standing tillering and removing the water phase, the organic phase was subjected to batch distillation to separate toluene, H-phenylaminocarbamate (72 g, 110TC, 3naiHg) and bis (ethoxycarbonylaminophenyl). Methane (30.1¾-180 t · lminHg) ° This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
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