1337603 Λ · _九、發明說明： * . 【發明所屬之技術頜域】 本發明係關於3級胺之製造方法。 【先前技術】 以3級胺之製造方法而言’已知有使用醇類或環狀醚 類為原料，在1級胺或2級胺與觸媒之存在下，於高溫高 壓下脫水’即所謂的氣相反應（例如專利文獻1)。又有提 案為將酿胺化合物於高溫高壓下，經觸媒氫化作用而製造 ^級胺乏方法（例如專利文獻^)。 [專利文獻1]日本特開平04-342578號公報 [專利文獻2]曰本專利第2553049號 此專利文獻1及2之方法，必須有高溫反應或高壓反 應等特殊之反應容器，無法在平穩之條件下實施。 以在平穩條件下之反應而言，有使2級胺函化烧基反 應之方法。的確，其雖為在常溫下之反應，但有將反應後 •成之i化氫予以中和的必要，所使用之鹼會與鹵化烧基 反應而使收率降低。又，—般而言，所生成之3級胺對鹵 化烧基之反應性比2級胺佳，會進行反應至4級鹽’而使 反應系統中混合存在菩2 Βίχ» 什隹者Ζ級胺、3級胺、4級胺。並非只是 反應收率不佳，取出之收率亦大幅降低，故為不佳。又，3 級胺與2級胺之分離通常藉由蒸館而精製，但尤其是在甲 土化反應巾3㈣與作為原料之2級胺 不大的化合物為多，故多右南山 七 难占差並 情形。 有取出之收率降低或工時增加等 318909 6 1337603 本發明之課題係提供以一般之反應裝置，在平穩之條 件下，不使原料殘留並定量.地使反應完成的3級胺之製造 方法。 【發明内容】 本發明係有關於以下之發明。 1. _種式（3)所示之3級胺之製造方法，其特徵為：將式（？） 所示之化a物添加至式（1)所示之化合物（或其聚合物）與 曱酸的混合物中 01337603 Λ · _9, invention description: *. [Technical jaw region to which the invention pertains] The present invention relates to a method for producing a tertiary amine. [Prior Art] In the production method of a tertiary amine, it is known that an alcohol or a cyclic ether is used as a raw material, and dehydration is carried out under high temperature and high pressure in the presence of a primary amine or a secondary amine and a catalyst. A so-called gas phase reaction (for example, Patent Document 1). Further, it has been proposed to produce a amide-depleted method by hydrogenation of a catalyst under high temperature and high pressure (e.g., Patent Document ^). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2,530, 049. Implemented under conditions. In the case of the reaction under a stable condition, there is a method of reacting a 2-stage amine functional group. Indeed, although it is a reaction at normal temperature, it is necessary to neutralize the hydrogenated hydrogen after the reaction, and the base to be used reacts with the halogenated alkyl group to lower the yield. In addition, in general, the generated tertiary amine is more reactive to the halogenated alkyl group than the secondary amine, and will react to the 4-stage salt', so that the reaction system is mixed with the Bodhisattva 2 Β χ χ Amine, tertiary amine, grade 4 amine. Not only the reaction yield is not good, but the yield of the removal is also greatly reduced, so it is not good. Further, the separation of the tertiary amine and the secondary amine is usually carried out by steaming, but especially in the case of the soiled reaction towel 3 (four) and the compound which is not a large amount of the second-order amine as a raw material, the multi-right Nanshan seven-difficulty Poor and situation. There is a decrease in yield or an increase in man-hours, etc. 318909 6 1337603 The object of the present invention is to provide a method for producing a tertiary amine which can be carried out in a general reaction apparatus under stable conditions without leaving a raw material and quantifying the reaction. . SUMMARY OF THE INVENTION The present invention relates to the following invention. 1. A method for producing a tertiary amine represented by the formula (3), characterized in that a compound represented by the formula (?) is added to a compound represented by the formula (1) (or a polymer thereof) and In a mixture of tannic acid 0
(式中 表示氫原子、Cl至C3之烷基）(wherein represents a hydrogen atom, an alkyl group of Cl to C3)
(2) (式t ’ R1及R2表示Ci至。之烷基；可藉由 及氮原子而形成環） ch2r3 (3) (式中，R至R3係與上述相同）。 2·如第1項之製造方沬 ..^ - 有心定環之化合物其㈣式⑺所^化合物係具 3’如第1項之製造方法’其中’該3級胺係恥曱基 本發明係將式（2)所示之化合物添加至式⑴所示各:化 318909 7 1337603 N - •-""勿（或其聚合物）與甲酸的混合物中的式（3)所干 .胺之製造方法。 ")所-之3級 R所示之基，具體而言係如下述。可列舉 甲基、乙基'正丙基、異丙基、環丙基等，又以=、 曱基為較佳。 子、 R至R2所示之基，具體而言係如下述。(2) (Formula t ' R1 and R2 represent an alkyl group of Ci to; a ring may be formed by a nitrogen atom) ch2r3 (3) (wherein R to R3 are the same as described above). 2. The manufacturing method of the first item: . . . - the compound of the heart-ringing compound, the compound of the formula (7), the compound of the formula (3), the manufacturing method of the first item, wherein the third-stage amine system of the basic invention of the shame The compound represented by the formula (2) is added to the compound of the formula (1): 318909 7 1337603 N - • - ""Do not (or its polymer) and the formic acid in the mixture of the formula (3) Manufacturing method. ") - Level 3 The base shown by R, specifically as follows. The methyl group, the ethyl 'n-propyl group, the isopropyl group, the cyclopropyl group and the like may be mentioned, and the = and fluorenyl groups are preferred. The group represented by the sub, R to R2 is specifically as follows.
Ci至G之烷基，可列舉如曱基、乙基、正丙基、異丙 拳基丙基等碳數1 i 3之直鍵狀、支鏈狀或環狀之垸基。 二平乂住之烷基而言，以碳數丨至3之直鏈狀烷基為較佳。 .藉由R1、R2及氮原子可形成5至7員之環。具體而言可例 节如比落〇疋、尚旅唆（H〇m〇piperidine)、0底〇定、略哄、嗎 啉等環。 ’ ’ 式U )所示之化合物，具體而言係如下述。可列舉如甲 醛、乙醛、丙醛、丁醛、異丁醛、三聚曱醛、三聚乙醛等。 又’其聚合物可列舉如三聚曱搭、三聚乙搭等。 φ 式（2)所示之化合物，具體而言係如下述。可列舉如二 曱基胺、二乙基胺、二丙基胺、二異丙基胺、甲基乙基胺、 曱基丙基胺、乙基丙基胺、曱基異丙基胺、乙基異丙基胺、 0比0各57疋、為σ底σ定、α底咬、π辰Π井、嗎琳等。 式（3 )所示之3級胺，例如列舉如三曱基胺、三乙基胺、 二乙基曱基胺、曱基二丙基胺、曱基二異丙基胺、乙基二 曱基胺、二曱基丙基胺、乙基甲基丙基胺、乙基曱基異丙 基胺、甲基吡咯啶、乙基吡咯啶、丙基吡咯啶、異丙基吡 咯啶、丁基吡咯啶、第三丁基吡咯啶、甲基高哌啶、乙基 318909 8 Ϊ337603 __南哌啶、曱基哌啶、乙基哌啶、二曱基哌哄、二乙基哌哄、 甲基乙基σ底哄、曱基嗎咐、、乙基嗎琳等。 本發明之製造方法，具體而言係如下述。 在備有回流冷凝器之反應容器内，混合式（1)所示之化 合物及甲酸。式（1)所示之化合物及曱酸亦可以水溶液而使 用。尤其是在使用低沸點之甲醛、乙醛時，以水溶液或以 聚合物而使用為較佳。甲醛之水溶液之濃度為2〇至5〇0/〇， ⑩又以30至40%為較佳。乙醛之水溶液之濃度為5〇至95〇/〇， 又以70至90%為較佳。甲酸水溶液之濃度為⑽至1〇〇%， 又以8 0 %以上為較佳。 一式（1)之化合物與甲酸的混合比例，曱酸相對於式 所不之化合物1莫耳為h 〇至5. 〇莫耳，又以2 〇至4. 〇 莫耳為較佳。當甲酸未達1〇莫耳時，作為原料之式⑵ 所不之化合物會有殘存之虞，又，將式⑵之化合物以烧基 ^甲基聯繫之副產物會大量產生。例如式⑵所示之化合物 啶時’會產生二如…定基甲烷之副產物;而如為 :甲基胺時，會大量產生四甲基二胺基甲烷之副產物。當 二時，"時所使用之鹼量必須變多’不僅不 -亦八加水層量而使目的物之回收率有降低之虞。 相對3)所示之化合物與式⑴所示之化合物的莫耳比， "至式⑵所不之化合物1莫耳式⑴所示之化合物為 示之化人物tT又以U至2, 5莫耳為較佳。當式⑴所 物會有：未達U旲耳時’作為原料之式⑵所示之化合 會有殘存之虞。當超過3.G莫耳時，未反應之式⑴之化 318909 9 13376〇3 合物=量殘存，於取出時會有使精製變得困難之虞。 之作：者’ #上述混合物加熱。加熱溫度可隨著式⑴所示 :物之種類而適當調節，但通常以4G至12代之範圍 ^此尤其以加熱至回流溫度為更佳。雖然會受所使用 席枓之沸點影塑，彳曰A τ 且认山 β —為了使所添加之胺會瞬間反應，而盡 二：溫下進行為理想。以低溫愿合3成分並昇溫之反應 二θ急遽地進行反應，依據反應熱與脫⑶2之平衡而有 /、/弗之可能而極其危險。 曰入然後，-邊回流一邊將式⑵所示之化合物添加至上述 二:谷液卜所添加之2級胺，亦特別限於低彿點者係以 液狀I、使用為較佳。濃度為3〇至⑽，又以㈣至㈣ =較佳。由於其反應為放熱反應，為了不引起急遽之反應， 二，可列舉例如滴下方法、細流添加方法等。添加時 曰Tik者混合溶液之量而適當調節，通常相對於所添加之 ，全量(1_)為5至5〇%，h，又以i。至3麟左 ^為較佳。當添加速度超過5G%/h時，依據反應熱與脫 C〇2之平衡而有暴沸之可能而極為危險。 ’】’、加、、、。東後’》了使反應完全進行而繼續加熱回流。 反應溫度可隨著反應混合物之種類而適當調節，通常以 至败之範圍為較佳，又以回流溫度為更佳。反應時間 可隨著混合物之量而適當調節，通常為！至24小時，以i 至12小時為較佳，又以2至8小時為更佳。 ，反應完成後，將反應溶液冷卻到1〇至5〇t。冷卻方 法以水冷卻法為較佳。 3]8909 10 ' 〜部後，添加鹼，分離有機層與水層。所添加之鹼劑 / ^用氫氧化鈉、氫氧化鉀、碳酸鈉' 碳酸鉀、氫氧化鋰、 ^經或該等之水溶液。尤其以氫氧仙、氫氧化卸、或 。亥等之水浴液為較佳。添加之鹼量以固體鹼濃度/全量引〇 ^ 50¾為較佳。添加溫度以室溫至6〇。〇左右為較佳。3級 胺被刀離於有機層，若鹼添加量過少’則不僅無法充分地 分離為2層，而即使分離為2層，其目的之胺對於有機層 鲁之分配率因降低而不佳。可依需要而以#機溶媒萃取。有 機’谷媒5使甩各種有機溶媒。一般而言可列舉如烴類、鹵 化溶媒、醚類。萃取後，藉由蒸餾而得到目的物。蒸餾時， 為了使精製容易進行，選擇所萃取之胺之沸點與萃取溶媒 之沸點的差距為大者。當萃取低沸點之胺時，以高沸點之 烴溶媒等為適合。又，當萃取高沸點之胺時，以選擇低沸 點之系或鹵化溶媒為較佳。 【實施方式】 # 以下，基於實施例而具體說明本發明，但不受此等限 制。又’在實施例及比較例中’以下述方法進行各種物性 之測定。 3級胺之鑑定 3級胺係由1H-NMR之測定結果所鑑定。原料之殘存量 及3級胺之收率係以氣相層析（gas chr〇matography，即 GC)決定。The alkyl group of Ci to G may, for example, be a straight-chain, branched or cyclic fluorenyl group having a carbon number of 1 i 3 such as a mercapto group, an ethyl group, a n-propyl group or an isopropylidene group. In the case of the alkyl group of the bismuth, it is preferred to use a linear alkyl group having a carbon number of 丨3. A ring of 5 to 7 members can be formed by R1, R2 and a nitrogen atom. Specifically, for example, a ring such as 〇疋 〇疋, 〇 〇 per (H〇m〇piperidine), 〇 bottom, slightly 哄, morpholine, and the like. The compound represented by the formula U) is specifically as described below. For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, trimeric furfural, paraldehyde or the like can be mentioned. Further, the polymer may, for example, be a trimeric oxime or a trimeric conjugate. The compound represented by the formula (2) is specifically as follows. Examples thereof include didecylamine, diethylamine, dipropylamine, diisopropylamine, methylethylamine, mercaptopropylamine, ethylpropylamine, mercaptoisopropylamine, and B. Isopropylamine, 0 to 0, each 57 疋, is σ σ σ, α bottom bite, π Π Π, 吗 等 and so on. The tertiary amine represented by the formula (3) is exemplified by, for example, tridecylamine, triethylamine, diethyldecylamine, decyldipropylamine, decyldiisopropylamine, ethyldifluorene. Base amine, dimercaptopropylamine, ethylmethylpropylamine, ethylmercaptoisopropylamine, methylpyrrolidine, ethylpyrrolidine, propylpyrrolidine, isopropylpyrrolidine, butyl Pyrrolidine, tert-butyl pyrrolidine, methyl homopiperidine, ethyl 318909 8 Ϊ 337603 __South piperidine, mercapyl piperidine, ethyl piperidine, dimercapto piperazine, diethyl piperazine, A Base ethyl σ bottom 曱, 曱 咐 咐, ethyl 琳 等 and so on. The production method of the present invention is specifically as follows. The compound of the formula (1) and formic acid were mixed in a reaction vessel equipped with a reflux condenser. The compound represented by the formula (1) and citric acid can also be used in the form of an aqueous solution. In particular, when a low boiling point of formaldehyde or acetaldehyde is used, it is preferably used in the form of an aqueous solution or a polymer. The concentration of the aqueous solution of formaldehyde is from 2 〇 to 5 〇 0 / 〇, and 10 is preferably from 30 to 40%. The concentration of the aqueous solution of acetaldehyde is from 5 Å to 95 Å/Torr, and preferably from 70 to 90%. The concentration of the aqueous formic acid solution is preferably from (10) to 1% by weight, and more preferably 80% by weight. The mixing ratio of the compound of the formula (1) to the formic acid is preferably h 耳 5 相对 相对 相对 相对 , , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. When the formic acid is less than 1 mole, the compound of the formula (2) which is a raw material may have a residual enthalpy, and a by-product of the compound of the formula (2) which is linked to the alkyl group may be produced in a large amount. For example, when the compound of the formula (2) is pyridine, a by-product such as a base methane is produced; and if it is a methylamine, a by-product of tetramethyldiaminomethane is produced in a large amount. At 2 o'clock, the amount of alkali used in the "should be increased" is not only not - but also the amount of water added to reduce the recovery rate of the target. The molar ratio of the compound shown in 3) to the compound represented by the formula (1), "to the compound of the formula (2), the compound represented by the formula (1) is represented by the character tT and U to 2, 5 Moore is preferred. When the formula (1) contains: when the U 旲 ear is not reached, the compound represented by the formula (2) as a raw material may have a residual enthalpy. When it exceeds 3. G mole, the unreacted formula (1) 318909 9 13376 〇 3 compound = amount remains, which may cause difficulty in purification when taken out. The work: 'The above mixture is heated. The heating temperature can be appropriately adjusted depending on the kind of the substance represented by the formula (1), but is usually in the range of 4G to 12th generation. This is particularly preferable by heating to the reflux temperature. Although it will be affected by the boiling point of the used 彳曰, 彳曰A τ and recognizing the mountain β—in order to make the added amine react instantaneously, it is ideal to perform at a temperature of two. The reaction of mixing the three components at a low temperature and raising the temperature is violently carried out. It is extremely dangerous depending on the balance between the heat of reaction and the balance of (3)2. Further, the compound represented by the formula (2) is added to the above-mentioned two: the second-order amine to be added to the glutinous solution while refluxing, and it is also preferable to use it in the liquid form I. The concentration is from 3〇 to (10), and from (4) to (4) = preferably. Since the reaction is an exothermic reaction, in order not to cause an imminent reaction, for example, a dropping method, a trickle addition method, and the like can be mentioned. When adding, the amount of the 曰Tik mixed solution is appropriately adjusted, and is usually 5 to 5 %, h, and i with respect to the total amount (1_) added. To 3 Lin Zuo ^ is better. When the addition rate exceeds 5 G%/h, it is extremely dangerous depending on the possibility of bumping depending on the balance between the heat of reaction and the removal of C〇2. '】',plus,,,. After the reaction, the reaction was completed and heating was continued to reflux. The reaction temperature can be appropriately adjusted depending on the kind of the reaction mixture, and it is usually preferred to be in the range of the yield, and more preferably the reflux temperature. The reaction time can be appropriately adjusted depending on the amount of the mixture, usually! For 24 hours, it is better to use i to 12 hours, and it is better to use 2 to 8 hours. After the reaction is completed, the reaction solution is cooled to 1 Torr to 5 Torr. The cooling method is preferably a water cooling method. 3] 8909 10 ' After the portion, add alkali, separate the organic layer from the aqueous layer. The alkali agent added / ^ using sodium hydroxide, potassium hydroxide, sodium carbonate 'potassium carbonate, lithium hydroxide, ^ or these aqueous solutions. Especially with oxyhydroxide, hydrazine dehydration, or . A water bath such as Hai is preferred. The amount of alkali added is preferably Zn 503⁄4 in terms of solid alkali concentration/full amount. Add temperature to room temperature to 6 Torr. It is better to be around. The tertiary amine is separated from the organic layer by a knife, and if the amount of the base added is too small, it is not sufficiently separated into two layers, and even if it is separated into two layers, the amine of the target is less preferable because the distribution ratio of the organic layer is lowered. It can be extracted by #machine solvent as needed. There is a machine '谷媒5 makes a variety of organic solvents. Generally, hydrocarbons, halogenated solvents, and ethers are exemplified. After the extraction, the object was obtained by distillation. At the time of distillation, in order to facilitate the purification, the difference between the boiling point of the extracted amine and the boiling point of the extraction solvent is selected to be large. When a low-boiling amine is extracted, a hydrocarbon solvent having a high boiling point or the like is suitable. Further, when extracting a high-boiling amine, it is preferred to select a low boiling point or a halogenated solvent. [Embodiment] # Hereinafter, the present invention will be specifically described based on examples, but is not limited thereto. Further, in the examples and comparative examples, various physical properties were measured by the following methods. Identification of the tertiary amine The tertiary amine was identified by the 1H-NMR measurement. The residual amount of the raw material and the yield of the tertiary amine are determined by gas chromatography (GC).
Ή-NMR ** BRUKER 300MHz GC ： SHIMADZU GC14B 318909 11 1337603 使用管柱：Ami pack 141 (GL Sciences 公司製） f施例1 N-甲某咐^各。定之製造 在備有回流冷凝器之1L之四口燒瓶中，加入37%甲醛 水溶液（和光純藥工業股份公司製）339. 65g(2. 95mol)、與 90%曱酸水溶液377.65g(7.38mol)。昇溫至回流溫度（85 C )。藉由滴液漏斗將吡咯咬（py) 1 75. 00g(2. 46mol)耗費約 5小時滴下。滴下皆於回流下進行。滴下結束後，於回流 _下（104°C )使其反應6小時（反應收率99%，吡咯啶殘存率 3%)。冷卻至室溫後’以内溫不會超過55。〇之方式，將 48%NaOH水溶液625g —邊冷卻一邊添加。將分離為2層之 有機層（上層）萃取。將上層214.46g(回收率98%，有機層 組成：N-甲基吡咯啶94. 7% ' PyO. 3% ' MeOH(甲醛之安定 劑）〇. 6%、H2〇4, 4%)進行蒸餾，得到曱醇5〇ppm以下、吡咯 啶50ppm以下、KhO 50ppm以下的N-曱基吡咯啶201. 23g (96%)。藉由1H-NMR確認目的物。 #H-NMR(D2〇) 占】.61(m 4H)，2. 14(s 3H)，2. 34(m 4H) 貫施例2至1 2 將吡咯啶（Py)、甲醛（HCH0)及甲酸（HC〇〇H)，以表i 所記載之比例、滴下時間、反應時間，於回流下使其反應。 得到目的之N-曱基^各。定（NMp)。蒸德後之收率顯示於表 卜又，任一實施例之原料Py之殘存量皆為5〇_以下。 又’在實施例2是使用三聚甲駿（和光純藥工業股份公司 製），在貫施例3則是放慢Py之添加速度。 318909 12 1337603 [表1 ] 實施例 Py HCHO HCOOH . '—------ 滴下時間 反應時間 蒸餾後收率 (hr) (hr) NMP ~' 2 1.0 1. 2 2. 5 --~~-. 6 18 82 — 3 1.0 1.2 2. 5 10 14 --丨 88 4 1. 0 1.2 2. 0 6 18 ' 1 *------ 84 5 1.0 1.2 3. 0 6 — 18 93 6 1.0 2. 0 3. 0 6 18 89 7 1.0 2. 0 2. 5 6 18 92 8 1.0 2. 0 2. 0 6 18 83 9 1.0 2. 0 1.5 6 ”18 — 86 10 1.0 1.2 3. 0 6 6 93 11 1.0 1.2 3. 0 7 3 *~—-_. 91 12 1.0 1.2 3. 0 2. 5 2 ----- 91 實施例13 除了將曱醛（2. 95mol)變更為乙醛（和光純藥工業股份 公司製，90%製品）（2. 95mol)以外，與實施例1進行相同操 籲作’得到N-乙基吡咯啶（蒸餾後收率95%，吡咯啶5〇ppm 以下）。 比較例1 除了將曱酸添加至吡咯啶及曱醛之混合溶液中以外， 與實施例1進行相同操作，製造N—甲基吡咯啶。反應收率 為56%，取出收率為2〇%(與吡咯啶之分離性不佳，取出收 率大巾田降低，又確認副產物之二_N_吡咯啶基曱烧產生 20%之量）。 交例2 318909 13 133.7603 除了將曱盤添加至3比咯啶及甲酸之混合溶液中以外， 與貫施例1進行相同操作，製造N_甲基吡咯啶。反應收率 為75% ’取出收率為55%(與吡咯啶之分離性不佳，取出收 率大幅降低）。 比較例3 在備有回流冷凝器之丨L之四口燒瓶中，加入吡咯啶 100. 〇〇g(l. 41mol)與碳酸鉀 97. 17g(〇· 70m〇1)、甲醇 /OOml’冷卻至ot；。將峨甲烧簡56g(148m〇i)以不會使 反應溫度超過5t：之方式緩慢地滴下。滴下結束後， 地昇溫，在2代反應10小時，在回流下反應1〇小時（反 應收半，料㈣存率27%)ι然藉由㈣ 但難以與原料完全分離。 夂 L「產業上之可利用性] 依據本發明，可在溫和之條件下，幾 級胺。 里吧衣迈3 令所含作為原料 例如可使其成為 > 又，依據本發明，可使目的之3級胺 之式（2)所示之化合物之殘存量成為微量， 1 OOppm以下’更佳為5〇ppm以下。 318909 14Ή-NMR ** BRUKER 300MHz GC : SHIMADZU GC14B 318909 11 1337603 Use of the column: Ami pack 141 (manufactured by GL Sciences) f Example 1 N-A certain 咐^ each. Manufactured in a 1 L four-necked flask equipped with a reflux condenser, 339.65 g (2.99 mol) of a 37% aqueous formaldehyde solution (manufactured by Wako Pure Chemical Industries, Ltd.), and 377.65 g (7.38 mol) of a 90% aqueous solution of citric acid. ). Warm to reflux (85 C). The pyrrole bite (py) 1 75. 00 g (2.646 mol) was dropped by a dropping funnel for about 5 hours. The dropping was carried out under reflux. After completion of the dropwise addition, the mixture was reacted under reflux (104 ° C) for 6 hours (reaction yield 99%, pyrrolidine residual ratio 3%). After cooling to room temperature, the internal temperature does not exceed 55. In the manner of 〇, 625 g of a 48% aqueous NaOH solution was added while cooling. The organic layer (upper layer) separated into two layers was extracted. The upper layer was 214.46 g (recovery rate 98%, organic layer composition: N-methylpyrrolidine 94.7% 'PyO. 3% ' MeOH (formaldehyde stabilizer) 〇. 6%, H2 〇 4, 4%) Distilled to give N-mercaptopyrrolidine 201.23 g (96%) of decyl alcohol 5 〇 ppm or less, pyrrolidine 50 ppm or less, and KhO 50 ppm or less. The object was confirmed by 1 H-NMR. #H-NMR(D2〇) 占】.61(m 4H), 2. 14(s 3H), 2. 34(m 4H) Example 2 to 1 2 Pyrrolidine (Py), Formaldehyde (HCH0) And formic acid (HC〇〇H) was reacted under reflux at the ratios indicated in Table i, the dropping time, and the reaction time. The desired N-mercapto group is obtained. Set (NMp). The yield after steaming is shown in the table, and the residual amount of the raw material Py in any of the examples is 5 Å or less. Further, in the second embodiment, the use of the tripoly group (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and in the third embodiment, the rate of addition of Py was slowed down. 318909 12 1337603 [Table 1] Example Py HCHO HCOOH . '------- Drip time Reaction time Distillation yield (hr) (hr) NMP ~' 2 1.0 1. 2 2. 5 --~~ -. 6 18 82 — 3 1.0 1.2 2. 5 10 14 --丨88 4 1. 0 1.2 2. 0 6 18 ' 1 *------ 84 5 1.0 1.2 3. 0 6 — 18 93 6 1.0 2. 0 3. 0 6 18 89 7 1.0 2. 0 2. 5 6 18 92 8 1.0 2. 0 2. 0 6 18 83 9 1.0 2. 0 1.5 6 ”18 — 86 10 1.0 1.2 3. 0 6 6 93 11 1.0 1.2 3. 0 7 3 *~--_. 91 12 1.0 1.2 3. 0 2. 5 2 ----- 91 Example 13 except that furfural (2.95 mol) was changed to acetaldehyde (and In the same manner as in Example 1, except for the production of 90% of the product (90% product) (2. 95 mol), N-ethylpyrrolidine was obtained (the yield after distillation was 95%, and the pyrrolidine was 5 〇 ppm or less). Comparative Example 1 N-methylpyrrolidine was produced in the same manner as in Example 1 except that citric acid was added to a mixed solution of pyrrolidine and furfural. The reaction yield was 56%, and the extraction yield was 2〇. %(The separation with pyrrolidine is not good, the extraction yield is reduced, and the _N_pyrrolidinyl group of by-products is confirmed to be produced. 20%). Example 2 318909 13 133.7603 N-methylpyrrolidine was produced in the same manner as in Example 1 except that the disk was added to a mixed solution of 3 to pyridin and formic acid. 75% 'take-out yield was 55% (poor separation from pyrrolidine, the extraction yield was greatly reduced). Comparative Example 3 In a four-necked flask equipped with a reflux condenser, pyrrolidine 100 was added. 〇〇g (1.41 mol) and potassium carbonate 97.17g (〇·70m〇1), methanol/OOml' cooled to ot; burn the armor with 56g (148m〇i) so that the reaction temperature does not exceed 5t : The method is slowly dripped. After the completion of the dropping, the ground is heated, and the reaction is carried out for 10 hours in the 2nd generation, and the reaction is carried out under reflux for 1 hour (the reaction is half-haled, the feed rate of the material (4) is 27%), and it is difficult to completely complete with the raw materials. Separation. 产业L "Industrial Applicability] According to the present invention, several amines can be obtained under mild conditions. For example, it can be made into a raw material, for example, according to the present invention. The residual amount of the compound represented by the formula (2) of the objective tertiary amine can be made into a trace amount, and it is preferably 1 00 ppm or less. Below ppm. 318909 14