JPS63246352A - Production of 2-haloethylamine hydrohalide - Google Patents
Production of 2-haloethylamine hydrohalideInfo
- Publication number
- JPS63246352A JPS63246352A JP7750087A JP7750087A JPS63246352A JP S63246352 A JPS63246352 A JP S63246352A JP 7750087 A JP7750087 A JP 7750087A JP 7750087 A JP7750087 A JP 7750087A JP S63246352 A JPS63246352 A JP S63246352A
- Authority
- JP
- Japan
- Prior art keywords
- ethyleneimine
- hydrohalogenic acid
- addition salt
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000002140 halogenating effect Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- -1 amino alcohol hydrochloride Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IZQAUUVBKYXMET-UHFFFAOYSA-N 2-bromoethanamine Chemical compound NCCBr IZQAUUVBKYXMET-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- IRRTUEIEPNRYCS-UHFFFAOYSA-N 2-methylprop-1-en-1-imine Chemical compound CC(C)=C=N IRRTUEIEPNRYCS-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアミノエチル化剤として有用であり医薬、農薬
、染顔料、写真薬、樹脂改質剤等、中間体として広範な
用途を用する２−ハロエチルアミンハロゲン化水素酸塩
の製造方法に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention is useful as an aminoethylating agent and has a wide range of uses as an intermediate in medicines, agricultural chemicals, dyes and pigments, photographic agents, resin modifiers, etc. The present invention relates to a method for producing 2-haloethylamine hydrohalide.
詳しくは、エチレンイミンとハロゲン化水素酸との反応
による高純度２−へロエチルアミン、ハロゲン化水素酸
塩の製造方法に関する。Specifically, the present invention relates to a method for producing highly purified 2-heroethylamine and hydrohalide salts by reaction of ethyleneimine and hydrohalic acid.
（従来の技術と問題点）
ハロアルキルアミンの合成法としてはアミノアルコール
の塩素化による方法が一般的に知られている。この方法
のうち塩化チオニルを用いる米国特許第２，１６３，１
８１号明細書記載の方法が古くから知られ比較的低温で
高収率が得られるが、副生する亜硫酸ガスの処理の問題
や製品の着色等の問題を有する。(Prior Art and Problems) As a method for synthesizing haloalkylamines, a method using chlorination of amino alcohol is generally known. Among these methods, U.S. Pat. No. 2,163,1 using thionyl chloride
The method described in the specification of No. 81 has been known for a long time and can obtain high yields at relatively low temperatures, but it has problems such as processing of by-product sulfur dioxide gas and coloring of the product.
また、塩素化剤として三塩化リンを用いる方法も知られ
ているが、これらの塩素化剤を用いる方法は、塩素死刑
自体が高価であることと、副生物除去等によるコスト高
のため工業的に有利な方法とは言えない。In addition, methods using phosphorus trichloride as a chlorinating agent are also known, but these methods are not suitable for industrial use due to the high cost of chlorine itself and the high cost of removing by-products. It cannot be said that it is an advantageous method.
また、塩素化剤として塩化水素ガスを用い、アミノアル
コール塩酸塩と溶融状態で反応させる方法特開昭５８−
４１４８２号が提案されているが、この方法も高価な塩
化水素ガスを用い、又圧力容器を必要とすることより必
ずしも有利な方法とは言えない、一方エチレンイミンと
ハロゲン化水素酸による２−ハロエチルアミンの合成は
ハロゲンイオンと水酸基イオンの競争反応のため副生物
として２−ヒドロキシエチルアミンが生成することが知
られている。たとえば２．２−ジメチルエチレンイミン
と６Ｎ塩酸との反応を２５℃で行ったところ、り四口体
の収率が９０．４％であり１−アミノ−２−メチル−２
−プロパツールが１．３％生成したとの報告がある。（
Ｊ、Ａ、Ｃ，Ｓ、７７巻５１１３ページ）
（問題点を解決するための手段）
本発明者は上述の問題点を解決すべく研究を重ねた結果
、エチレンイミンとハロゲン化水素酸との反応により、
２−ハロエチルアミンハロゲン化水素酸塩を製造するに
際し、ハロゲン化水素酸中にエチレンイミンを１０℃以
下の温度で加え、エチレンイミンの開環を抑制し、ハロ
ゲン化水素酸との付加塩とした後、昇温し、開環ハロゲ
ン化を行なうことにより９８％以上の高純度の２−ハロ
エチルアミンハロゲン化水素酸塩が９８％以上の高収率
で得られることを発見し本発明に至った。In addition, a method is disclosed in which hydrogen chloride gas is used as a chlorinating agent and reacted with amino alcohol hydrochloride in a molten state.
No. 41482 has been proposed, but this method also uses expensive hydrogen chloride gas and requires a pressure vessel, so it is not necessarily an advantageous method. It is known that in the synthesis of ethylamine, 2-hydroxyethylamine is produced as a by-product due to a competitive reaction between halogen ions and hydroxyl ions. For example, when the reaction between 2,2-dimethylethyleneimine and 6N hydrochloric acid was carried out at 25°C, the yield of tetrahedral compound was 90.4%, and 1-amino-2-methyl-2
- It is reported that the property tool generated 1.3%. (
J, A, C, S, Vol. 77, p. 5113) (Means for solving the problem) As a result of repeated research to solve the above-mentioned problem, the present inventor has discovered that the combination of ethyleneimine and hydrohalic acid Due to the reaction,
When producing 2-haloethylamine hydrohalide, ethyleneimine was added to hydrohalic acid at a temperature of 10°C or lower to suppress ring opening of ethyleneimine and form an addition salt with hydrohalic acid. After that, they discovered that by raising the temperature and performing ring-opening halogenation, 2-haloethylamine hydrohalide with a high purity of 98% or more can be obtained in a high yield of 98% or more, leading to the present invention. .
本発明は、２倍モル以上のハロゲン化水素酸中に１０℃
以下の温度を維持しなからエチレンイミンを加え、エチ
レンイミンの開環を抑制しながら、エチレンイミンとハ
ロゲン化水素酸との付加塩としな後、昇温し開環ハロゲ
ン化を行なうことにより実施される。ハロゲン化水素酸
中にエチレンイミンを１０℃以下で加えることの意味は
ハロゲンイオンと水素基イオンの競争反応を抑え副生物
であるエタノールアミンの生成を抑制しハロエチルアミ
ンの選択性を上げることにある。又ハロゲン化水素酸の
濃度もハロエチルアミンの選択性に影響を与えることよ
り濃いハロゲン化水素酸の使用が好ましい、ハロゲン化
水素酸とエチレンイミンのモル比は、ハロゲン化及び生
成物の塩形成のなめ２倍モル以上必要である。２倍モル
以上あれば反応に関しては十分であるが、製品を粉体と
して得る場合濃縮工程が必要であるので、大過剰用いる
のは不経済であり、２．０内至２．２倍モルが好ましい
。In the present invention, in a hydrohalic acid of 2 times the mole or more,
This is carried out by adding ethyleneimine while maintaining the following temperature, forming an addition salt of ethyleneimine and hydrohalic acid while suppressing the ring opening of ethyleneimine, and then raising the temperature to perform ring-opening halogenation. be done. The purpose of adding ethyleneimine to hydrohalic acid at a temperature below 10°C is to suppress the competitive reaction between halogen ions and hydrogen group ions, suppress the production of ethanolamine as a by-product, and increase the selectivity of haloethylamine. . The concentration of hydrohalic acid also affects the selectivity of haloethylamine, so it is preferable to use concentrated hydrohalic acid. More than twice the mole amount is required. 2 times the mole or more is sufficient for the reaction, but if the product is obtained as a powder, a concentration step is required, so it is uneconomical to use a large excess; preferable.
本発明に使用するハロゲン化水素酸としては塩酸、臭化
水素酸、ヨウ化水素酸、フッ化水素酸が挙げられる。Hydrohalic acids used in the present invention include hydrochloric acid, hydrobromic acid, hydroiodic acid, and hydrofluoric acid.
反応は実質的にハロゲン化水素酸自身をハロゲン化剤お
よび溶剤として使用することにより実施される。ハロゲ
ン化水素酸として３８重量％塩酸水溶液、４７重量％臭
化水素酸水溶液をエチレン・イミンの２倍モル用いた時
対応する２−クロロエチルアミン、塩酸塩、及び２−ブ
ロモエチルアミン、臭化水素酸塩は約５０重量％の水溶
液として得られ通常水溶液そのままの形で次のアミノエ
チル化等の反応に供せられる。又粉体として必要な時は
反応液を濃縮後、晶析分離を行うかもしくは濃縮後アル
コールを加え晶析分離することにより簡単に純品の粉体
として得られる。The reaction is carried out essentially using the hydrohalic acid itself as the halogenating agent and solvent. When using 38% by weight aqueous hydrochloric acid solution and 47% by weight aqueous hydrobromic acid solution as hydrohalic acid, the corresponding 2-chloroethylamine, hydrochloride, and 2-bromoethylamine, hydrobromic acid The salt is obtained as an approximately 50% by weight aqueous solution, and is usually subjected to subsequent reactions such as aminoethylation in the form of an aqueous solution. When a powder is required, it can be easily obtained as a pure powder by concentrating the reaction solution and then performing crystallization separation, or by adding alcohol after concentration and performing crystallization separation.
ハロゲン化水素酸塩にエチレンイミンを１０℃以下で加
え、エチレンイミンとハロゲン化水素酸との付加塩とし
た後開環ハロゲン化させる際の温度は３０℃以下の時へ
ロエチルアミンの選択性にはそれ程影響しないが３０℃
を越えると、選択性が低下する傾向にあるので、１０〜
３０℃で実質的に反応を終了させるのが好ましい０反応
時間は１０〜３０℃の温度で５時間で十分であり、好ま
しくは１０〜３０℃の温度で１〜３時間保った後、３０
℃で２時間保つのがよい、わずかに残存する付加塩を実
質的になくすため最終的に７０°Ｃまで昇温することに
より実施される。Ethyleneimine is added to the hydrohalide salt at 10°C or lower to form an addition salt of ethyleneimine and hydrohalic acid, and then the ring-opening halogenation is performed at a temperature of 30°C or lower. does not have much effect, but 30℃
If it exceeds 10~, the selectivity tends to decrease.
The reaction time is preferably 5 hours at a temperature of 10 to 30 °C, and preferably 1 to 3 hours at a temperature of 10 to 30 °C, and then 30
This is preferably carried out by keeping the temperature at 70° C. for 2 hours, and finally increasing the temperature to 70° C. in order to virtually eliminate any remaining addition salts.
（効 果）
上記の如く本発明はハロゲン化剤として安価に入手出来
るハロゲン化水素酸を用い副生物の極めて少ない２−ハ
ロエチルアミンハロゲン化水素酸塩を高収率で得ること
のできる工業的に有利な製造法である。(Effects) As described above, the present invention is an industrial method that uses inexpensively available hydrohalic acid as a halogenating agent to obtain 2-haloethylamine hydrohalide with extremely few by-products in high yield. This is an advantageous manufacturing method.
（実 施 例）
以下実施例により本発明を具体的に説明するが、これら
の実施例は例示であり本発明はこれらに限定されるもの
ではない。(Examples) The present invention will be specifically described below with reference to Examples, but these Examples are illustrative and the present invention is not limited thereto.
実施例−１
かくはん機付フラスコに３８重厘％塩酸水溶液４０３．
４グラムを仕込み１０℃以下に冷却しな。Example-1 38% hydrochloric acid aqueous solution 403% in a flask with a stirrer.
Add 4 grams and cool to below 10℃.
このフラスコ中に１０℃以下を維持しながらエチレンイ
ミン８６グラムをかくはんしながら滴下した。この際エ
チレンイミンの添加に約１時間要した。エチレンイミン
の添加終了後、フラスコ内温を３時間かけ３０℃まで昇
温し、３０℃にて２時間保持した後最終的に７０’Ｃま
で昇温し反応を終了させた。86 grams of ethyleneimine was added dropwise into the flask with stirring while maintaining the temperature at 10° C. or lower. At this time, it took about 1 hour to add ethyleneimine. After the addition of ethyleneimine was completed, the internal temperature of the flask was raised to 30°C over 3 hours, maintained at 30°C for 2 hours, and finally raised to 70'C to terminate the reaction.
反応液の分析によると未反応のエチレンイミンは残存せ
ずエチレンイミンに対する２−クロロエチルアミン塩酸
塩の選択性（収率）は９８．７％であった。Analysis of the reaction solution revealed that no unreacted ethyleneimine remained and the selectivity (yield) of 2-chloroethylamine hydrochloride to ethyleneimine was 98.7%.
実施例−２
かくはん機付フラスコに４７重量％臭化水素酸水溶液３
６１．５グラムを仕込み１０℃以下に冷却しな、このフ
ラスコ中に１０℃以下を維持しなからエチレンイミン４
３グラムをかくはんしながら滴下した。この際エチレン
イミンの添加に約１時間要しな、以下実施例−１と同様
に昇温し反応を終了させた９反応液の分析によるとエチ
レンイミンは残存せずエチレンイミンに対する２−ブロ
モエチルアミン臭化水素酸塩の選択性（収率）は９９．
２％であった。Example-2 47% by weight hydrobromic acid aqueous solution 3 in a flask with a stirrer
Charge 61.5 grams of ethyleneimine 4 and cool it to below 10°C.
3 grams was added dropwise while stirring. At this time, it took about 1 hour to add ethyleneimine. However, analysis of 9 reaction liquids, which were heated and terminated in the same manner as in Example 1, revealed that no ethyleneimine remained, and 2-bromoethylamine relative to ethyleneimine The selectivity (yield) for hydrobromide is 99.
It was 2%.
比較例−１
かくはん機付フラスコに３８重量％塩酸水溶液４０３．
４グラムを仕込み、このフラスコ中に３０℃を維持しな
からエチレンイミン８６グラムをかくはんしながら滴下
しな、この際エチレンイミンの添加に約３０分を要した
。エチレンイミンの添加終了後、３０℃にて２時間保持
した後、最終的に７０″Ｃまで昇温し反応を終了させた
。Comparative Example-1 A 38% by weight hydrochloric acid aqueous solution 403% in a flask with a stirrer.
4 grams of ethyleneimine was added dropwise into the flask while maintaining the temperature at 30° C. while stirring, and it took about 30 minutes for the addition of ethyleneimine. After the addition of ethyleneimine was completed, the temperature was maintained at 30° C. for 2 hours, and the temperature was finally raised to 70″C to terminate the reaction.
反応液の分析によると未反応エチレンイミンは残存せず
、エチレンイミンに対する２−クロロエチルアミン塩酸
塩の選択性（収率）は９１．５％であり、実施例−１に
比教して低収率であった。According to analysis of the reaction solution, no unreacted ethyleneimine remained, and the selectivity (yield) of 2-chloroethylamine hydrochloride to ethyleneimine was 91.5%, which was lower than in Example 1. The rate was
Claims (1)
り、２−ハロエチルアミンハロゲン化水素酸塩を製造す
るに際し、ハロゲン化水素酸中にエチレンイミンを１０
℃以下の温度で加え、エチレンイミンの開環を抑制し、
ハロゲン化水素酸との付加塩とした後、昇温し、開環ハ
ロゲン化を行なわしめることを特徴とする２−ハロエチ
ルアミンハロゲン化水素酸塩の製造方法。(1) When producing 2-haloethylamine hydrohalide by the reaction of ethyleneimine and hydrohalic acid, 10% of ethyleneimine is added to the hydrohalic acid.
It is added at a temperature below ℃ to suppress the ring opening of ethyleneimine,
1. A method for producing 2-haloethylamine hydrohalide, which comprises forming an addition salt with hydrohalic acid, followed by heating and ring-opening halogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7750087A JPH0791240B2 (en) | 1987-04-01 | 1987-04-01 | Method for producing 2-haloethylamine hydrohalide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7750087A JPH0791240B2 (en) | 1987-04-01 | 1987-04-01 | Method for producing 2-haloethylamine hydrohalide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63246352A true JPS63246352A (en) | 1988-10-13 |
| JPH0791240B2 JPH0791240B2 (en) | 1995-10-04 |
Family
ID=13635688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7750087A Expired - Lifetime JPH0791240B2 (en) | 1987-04-01 | 1987-04-01 | Method for producing 2-haloethylamine hydrohalide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791240B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002504508A (en) * | 1998-02-24 | 2002-02-12 | レナーツ，ビンセント | Crosslinked high amylose starch with functional groups as sustained release matrix for drug |
-
1987
- 1987-04-01 JP JP7750087A patent/JPH0791240B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002504508A (en) * | 1998-02-24 | 2002-02-12 | レナーツ，ビンセント | Crosslinked high amylose starch with functional groups as sustained release matrix for drug |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791240B2 (en) | 1995-10-04 |
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