JPH0272142A - Production of chlorinated amine hydrochloride - Google Patents
Production of chlorinated amine hydrochlorideInfo
- Publication number
- JPH0272142A JPH0272142A JP15485288A JP15485288A JPH0272142A JP H0272142 A JPH0272142 A JP H0272142A JP 15485288 A JP15485288 A JP 15485288A JP 15485288 A JP15485288 A JP 15485288A JP H0272142 A JPH0272142 A JP H0272142A
- Authority
- JP
- Japan
- Prior art keywords
- thionyl chloride
- amino
- alcohol
- amino alcohol
- 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.)
- Pending
Links
- -1 amine hydrochloride Chemical class 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000001414 amino alcohols Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 6
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract 6
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAZNWLZCASYNFC-UHFFFAOYSA-N 1-(2-chloroethyl)-4-methylpiperidine;hydrochloride Chemical compound [Cl-].CC1CC[NH+](CCCl)CC1 PAZNWLZCASYNFC-UHFFFAOYSA-N 0.000 description 1
- VFLQQZCRHPIGJU-UHFFFAOYSA-N 1-(2-chloroethyl)piperidine;hydron;chloride Chemical compound Cl.ClCCN1CCCCC1 VFLQQZCRHPIGJU-UHFFFAOYSA-N 0.000 description 1
- DZWJRQPMTHONRZ-UHFFFAOYSA-N 2-(4-methylpiperidin-1-yl)ethanol Chemical compound CC1CCN(CCO)CC1 DZWJRQPMTHONRZ-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QQCGKIZHTJLRNN-NBRVCOCJSA-N Pipericine Chemical compound CCCCCCCCCCCCC\C=C\C=C\C(=O)NCC(C)C QQCGKIZHTJLRNN-NBRVCOCJSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UTWYCVYPCQKRDR-UHFFFAOYSA-N n-methyl-n-phenylhydroxylamine Chemical compound CN(O)C1=CC=CC=C1 UTWYCVYPCQKRDR-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 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、塩素化アミン塩酸塩の製造方法、詳しくは、
高純度の塩素化アミン塩酸塩を収率よ〈製造する方法に
関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing chlorinated amine hydrochloride, in particular,
This invention relates to a method for producing high purity chlorinated amine hydrochloride in terms of yield.
（従来の技術）
塩素化アミン塩酸塩は、医農薬等の工業■品の中間体と
して重要な化学製品である。従来、塩素化アミン塩酸塩
は、アミノアルコールの有機溶媒溶液に塩化チオニルを
添加し、アミノアルコールと塩化チオニルを反応させる
ことにより製造されてｂた〔ジャーナル・オブ・サイエ
ンティフィック・アンド・インダストリアル・リサーチ
・セフシラン・ビー（Ｊｏｕｒｎａｌ ｏｆ ５ｃｉｅ
ｎｔｉｆｉｃ ａｎｄＩｎｄｕｓｔｒｉｍｌ Ｒｅ５ｅ
ａｒｃｈ ５ｅｃｔｉｏｎ Ｂ ）第１７巻、第１１〜
１５頁（１９５８年）〕。(Prior Art) Chlorinated amine hydrochloride is an important chemical product as an intermediate for industrial products such as medicines and agrochemicals. Conventionally, chlorinated amine hydrochloride was produced by adding thionyl chloride to an organic solvent solution of an amino alcohol and reacting the amino alcohol with thionyl chloride [Journal of Scientific and Industrial Research Cefsilane Bee (Journal of 5cie)
ntific andIndustry Re5e
arch 5ection B) Volume 17, Volume 11~
15 pages (1958)].
（発明が解決しようとする課題）
しかしながら、上記の従来法によって製造された塩素化
アミン塩酸塩は、原料の塩化チオニル中の硫黄分が不純
物として混入するため、純度が非常圧低かった。しかも
、この硫黄分によシ黄色ないし茶色に着色するため、商
品価値が低下していた。(Problems to be Solved by the Invention) However, the chlorinated amine hydrochloride produced by the above conventional method had extremely low purity because the sulfur content in the raw material thionyl chloride was mixed in as an impurity. Moreover, the sulfur content causes the product to turn yellow or brown, reducing its commercial value.
したがって、無着色で純度の高い塩素化アミン塩酸塩を
得るためには、再結晶操作が必要であった。しかし、再
結晶操作が製造工程に加わることにより、塩素化アミン
塩酸塩の収率は低下し、製造コストは上昇した。Therefore, a recrystallization operation was necessary to obtain uncolored and highly pure chlorinated amine hydrochloride. However, by adding a recrystallization operation to the manufacturing process, the yield of chlorinated amine hydrochloride decreased and the manufacturing cost increased.
（課題を解決するための手段）
本発明者等は、塩素化アミン塩酸塩の製造方法について
鋭意研究を重ねた結果、塩化チオニルにアミノアルコー
ルを添加することによシ、高純度かつ無着色の塩素化ア
ミン塩酸塩を収率よく製造し得ることを見すだし、本発
明を完成するに至った。(Means for Solving the Problems) As a result of extensive research into the production method of chlorinated amine hydrochloride, the present inventors have discovered that by adding an amino alcohol to thionyl chloride, a highly pure and uncolored product can be produced. It was discovered that chlorinated amine hydrochloride can be produced with good yield, and the present invention was completed.
本発明は、塩化チオニルにアミノアルコールを添加して
反応させることを特徴とする塩素化アミン塩酸塩の製造
方法である。The present invention is a method for producing chlorinated amine hydrochloride, which is characterized by adding an amino alcohol to thionyl chloride and causing the reaction.
本発明に於込て、塩化チオニルは、そのまま或いは有機
溶媒で希釈されて使用される。塩化チオニルを希釈する
有機溶媒は、塩化チオニルと反応しなければ、公知の有
機溶媒を特に限定せずに使用し得る。例えば、四塩化炭
素、クロロホルム、ジクロロエタン、塩化メタンなどの
塩素系溶媒；ベンゼン、トルエン、キシレン、クロロベ
ンゼンなどの芳香族系溶媒等が挙げられる。本発明に於
いては、塩化チオニルと、後述するアミノアルコールの
反応を温和に行なうために、塩化チオニルを有機溶媒で
５〜４０重量優に希釈することが好ましい。In the present invention, thionyl chloride is used as it is or diluted with an organic solvent. As the organic solvent for diluting thionyl chloride, any known organic solvent can be used without particular limitation as long as it does not react with thionyl chloride. Examples include chlorinated solvents such as carbon tetrachloride, chloroform, dichloroethane, and chlorinated methane; aromatic solvents such as benzene, toluene, xylene, and chlorobenzene. In the present invention, in order to mildly carry out the reaction between thionyl chloride and the amino alcohol described below, it is preferable to dilute thionyl chloride by 5 to 40% by weight with an organic solvent.
本発明で使用するアミノアルコールは第一アミノ基（−
ＮＨ２） 、第ニアミノ基（＞ＮＨ）又は第三アミノ基
（＞Ｎ−）のいずれかを有し、且水酸基（−ＯＨ）よび
Ｒ４は水素または１価の炭化水素残基を示し、互いに同
一でも異なっていても或いは両者が末端で結合していて
もよい。またＹは置換基を有するか又は有しない２価の
炭化水素残基を示す）と表すこともできる。これらの化
合物の具体的例は、例えば、メタノールアミン、エタノ
ールアミン、Ｎ−メチルメタノールアミン、Ｎ−ツメチ
ルメタノールアミン、Ｎ−ノエチルメタノールアミン、
Ｎ−グロビルエタノールアミン、ブタノールアミン、Ｎ
−メチルブタノールアミン、ペンタノールアミン、Ｎ−
ツメチルペンタノールアミン、オクタツールアミン、Ｎ
−ノプタノールオクタノールアミン等のＮ置換又は非置
換の脂肪族アルコールアミン類、同じくヒドロキシアニ
リン、Ｎ−メチルヒドロキシアニリン、Ｎ−ジメチルヒ
ドロキシアニリン、Ｎ−ジエチルヒドロキシアニリン、
Ｎ−ノペンチルヒドロキシアニリン等Ｎ［換又は非置換
の芳香族アミノアルコール類、アミンヘキシルアルコー
ル、Ｎ−ジメチルアミノヘキシルアルコール等のＮ置換
又は非置換のシクロアルキルアルコール類等である。一
般に前Ｙは炭素数１以上の２価の置換又は非置換の炭化
水素基であればよいが好ましくは炭素１０以下、更には
６以下の基である。The amino alcohol used in the present invention has a primary amino group (-
NH2), a secondary amino group (>NH) or a tertiary amino group (>N-), and the hydroxyl group (-OH) and R4 represent hydrogen or a monovalent hydrocarbon residue, and are the same as each other. However, they may be different, or both may be connected at their ends. Furthermore, Y represents a divalent hydrocarbon residue with or without a substituent. Specific examples of these compounds include methanolamine, ethanolamine, N-methylmethanolamine, N-tmethylmethanolamine, N-noethylmethanolamine,
N-globil ethanolamine, butanolamine, N
-Methylbutanolamine, pentanolamine, N-
trimethylpentanolamine, octatoolamine, N
-N-substituted or unsubstituted aliphatic alcohol amines such as noptanoloctanolamine, also hydroxyaniline, N-methylhydroxyaniline, N-dimethylhydroxyaniline, N-diethylhydroxyaniline,
These include N-substituted or unsubstituted aromatic amino alcohols such as N-nopentylhydroxyaniline, N-substituted or unsubstituted cycloalkyl alcohols such as aminehexyl alcohol, and N-dimethylaminohexyl alcohol. Generally, Y may be a divalent substituted or unsubstituted hydrocarbon group having 1 or more carbon atoms, but is preferably a group having 10 or less carbon atoms, more preferably 6 or less carbon atoms.
また一般に得られる塩素化アミン塩酸塩の収率及び純度
等を勘案すると、下記式＋１１及び（ＩＤで示されるア
ミノアルコールが好適に使用される。Furthermore, in consideration of the yield and purity of commonly obtained chlorinated amine hydrochloride, amino alcohols represented by the following formulas +11 and (ID) are preferably used.
（式中、Ｒ１およびＲ２は水素原子またはアルキル基を
示し、互いに同一でも異なっていてもよい。(In the formula, R1 and R2 represent a hydrogen atom or an alkyl group, and may be the same or different from each other.
また、ｍは１以上の整数好ましくは１〜１０の整数であ
る）
（式中、ｎは４または５であシ、ｍは１以上の整数好ま
しくは１〜１０の整数である）以下余白
上記したアミノアルコールの中でも、％に一般式（Ｉｔ
）で示される化合物を用いた場合には、よシ高収率で塩
素化アミン塩酸塩が得られるために好適である。In addition, m is an integer of 1 or more, preferably an integer of 1 to 10. (In the formula, n is 4 or 5, and m is an integer of 1 or more, preferably an integer of 1 to 10.) Among the amino alcohols, % of the general formula (It
) is preferable because chlorinated amine hydrochloride can be obtained in a very high yield.
アミノアルコールは、そのまま、或いは有機溶媒で希釈
して用すられるが、前記した塩化チオニルの場合と同様
に反応を温和に行なうために、有機溶媒で１０〜６０重
量係に希釈して用いることが好ましｈ０希釈のための有
機溶媒としては、塩化チオニルについて説明したものが
何ら制限なく採用される。Amino alcohol can be used as it is or diluted with an organic solvent, but as in the case of thionyl chloride, in order to carry out the reaction mildly, it can be diluted with an organic solvent to a concentration of 10 to 60% by weight. As the organic solvent for preferably ho dilution, those described for thionyl chloride are employed without any restriction.
本発明の最大の特徴は、塩化チオニルにアミノアルコー
ルを添加する点にある。これを逆にしてアミノアルコー
ルに塩化チオニルを添加しても本発明の効果は得られな
い。本発明の方法にょシ得られる塩素化アミン塩酸塩を
高純度で且つ無着色とするためには、反応液中に未反応
のアミノアルコールか大量に存在しないように、アミン
アルコールの添加をゆりく）行なうことが好ましい。通
常、このアミンアルコールの添加方法として滴下による
添加が好適に採用される。The greatest feature of the present invention is that an amino alcohol is added to thionyl chloride. Even if this is reversed and thionyl chloride is added to the amino alcohol, the effects of the present invention cannot be obtained. In order to make the chlorinated amine hydrochloride obtained by the method of the present invention highly pure and uncolored, the amine alcohol should be added slowly so that a large amount of unreacted amino alcohol does not exist in the reaction solution. ) is preferred. Usually, dropwise addition is suitably employed as the method of adding the amine alcohol.
本発明圧おける塩化チオニルとアミノアルコールの反応
は、理論的には、塩化チオニル１分子とアミノアルコー
ル１分子が反応して塩素化アよン塩酸塩１分子が生成す
る。したがって、塩化チオニルと７ミノアルコールの両
物質をできるだけ効率的に無駄なく使用するためには、
塩化チオニル１モルあたシのアミノアルコールの使用量
を０．８〜１．０モルとすることが好ましｂが、前記範
囲外の使用量でアミノアルコールを使用することも、当
然可能である。In the reaction between thionyl chloride and an amino alcohol under pressure according to the present invention, theoretically, one molecule of thionyl chloride and one molecule of amino alcohol react to produce one molecule of chlorinated amine hydrochloride. Therefore, in order to use both thionyl chloride and 7-minoalcohol as efficiently and without waste as possible,
It is preferable that the amount of amino alcohol used per mol of thionyl chloride is 0.8 to 1.0 mol b, but it is of course possible to use the amino alcohol in an amount outside the above range. .
ま之、塩化チオニルとアミノアルコールを反応させると
きの温度について、特に制限はないが、塩化チオニル、
アミノアルコールが気化しない温度範囲であることが好
ましく、例えば、０〜８０℃の範囲内とすることが好ま
しい。There are no particular restrictions on the temperature at which thionyl chloride and amino alcohol are reacted, but thionyl chloride,
The temperature range is preferably such that the amino alcohol does not vaporize, for example, preferably within the range of 0 to 80°C.
本発明の方法によシ製造された塩素化アミン塩酸塩は、
結晶として析出するため、反応液がスラリーとなり流動
性が悪くなることがある。このため、反応液中の塩素化
アミン塩酸塩の濃度を３５重量係以下となるように塩化
チオニル、アミノアルコールまたは有機溶媒を加えつつ
反応を行なうことが好ましい。The chlorinated amine hydrochloride produced by the method of the present invention is
Since it precipitates as crystals, the reaction solution may become a slurry and have poor fluidity. Therefore, it is preferable to carry out the reaction while adding thionyl chloride, an amino alcohol, or an organic solvent so that the concentration of chlorinated amine hydrochloride in the reaction solution becomes 35% by weight or less.
本発明において、塩化チオニルへのアミノアルコールの
添加開始時から反応終了時までの間、反応を速やかに進
めるために、反応液を攪拌することが好ましい。また、
空気中等にある不純物の混入や副反応による塩素化アミ
ン塩酸塩の純度の低下を防ぐため忙、反応液の気相部を
窒素等の不活性気体雰囲気とすることが好ましい。In the present invention, it is preferable to stir the reaction solution from the start of addition of the amino alcohol to thionyl chloride to the end of the reaction in order to speed up the reaction. Also,
In order to prevent the purity of the chlorinated amine hydrochloride from being degraded due to contamination with impurities in the air or side reactions, it is preferable to keep the gas phase of the reaction solution in an inert gas atmosphere such as nitrogen.
反応終了後、未反応の塩化チオニルおよび副生物である
二酸化硫黄等を、公知の方法例えば、減圧蒸留等の方法
により除去することが好ましい。After completion of the reaction, it is preferable to remove unreacted thionyl chloride and by-products such as sulfur dioxide by a known method such as vacuum distillation.
塩化チオニルおよび二酸化硫黄を除去した後の反応液を
遠心分離、濾過等によシ固液分離することにより塩素化
アミン塩酸塩を得ることができる。Chlorinated amine hydrochloride can be obtained by solid-liquid separation of the reaction solution after removing thionyl chloride and sulfur dioxide by centrifugation, filtration, or the like.
一般に、塩素化アミン塩酸塩の表面には、不純物が付着
しているため、塩化チオニルあるいはアミノアルコール
の希釈に使用する有機溶媒等によって洗浄し、乾燥する
ことが好ましい。Generally, since impurities adhere to the surface of chlorinated amine hydrochloride, it is preferable to wash it with an organic solvent used for diluting thionyl chloride or amino alcohol, and then dry it.
（効果）
本発明によれば、９９分以上の純度で無着色の塩素化ア
ミン塩酸塩を９０係以上の収率で製造し得る。この無着
色性は、従来の塩素化アミン塩酸塩の製造方法の場合よ
りも格段に高ｈ０しかも、従来法では、再結晶操作を行
う必要があったが、本発明によれば、その必要性はなく
なる。このように、本発明によれば、簡便に高純度かつ
無着色の塩素化アミン塩酸塩を高収率で製造することが
できる。(Effects) According to the present invention, uncolored chlorinated amine hydrochloride with a purity of 99 minutes or more can be produced with a yield of 90 factors or more. This color-free property is much higher h0 than in the case of the conventional production method of chlorinated amine hydrochloride. Moreover, in the conventional method, it was necessary to perform a recrystallization operation, but according to the present invention, the necessity for recrystallization is eliminated. will disappear. As described above, according to the present invention, highly pure and uncolored chlorinated amine hydrochloride can be easily produced in high yield.
（実施例）
以下に実施例および比較例を挙げる。なお、実施例およ
び比較例に於いて、塩素化アミン塩酸塩の無着色性は透
過率で示した。透過率Ｔ４５０ｎｍは、塩素化アミン塩
酸塩を水に溶かして調製した５重ｔ％濃度の塩素化アミ
ン塩酸塩水溶液を１ｃｆＲ角の石英セルに入れ、この石
英セルに４３０ｎｍ波長の光線を当てて測定した。(Example) Examples and comparative examples are listed below. In the Examples and Comparative Examples, the non-coloring property of chlorinated amine hydrochloride was expressed by transmittance. Transmittance T450nm is measured by placing a 5wt% chlorinated amine hydrochloride aqueous solution prepared by dissolving chlorinated amine hydrochloride in water into a 1 cfR square quartz cell, and shining a light beam of 430 nm wavelength onto the quartz cell. did.
実施例１
ジクロロエタン３７１．１６ｇに塩化チオニル８０、２
８．９を溶解し、塩化チオニル溶液を調製した。別に、
ゾクｏｏエタ７８５．５０．ＦＫｌ−（２−ヒドロキシ
エチル）ピペリジン８６．３３ ｇを溶解し、１−（２
−ヒドロキシエチル）ピ（リジン溶液を調製した。次に
、窒素気流下において、塩化チオニル溶液を攪拌しなが
ら、この塩化チオニル浴液に１−（２−ヒドロキシエチ
ル）ピペリジン溶液全量を１時間かけて滴下した。滴下
終了後、さらに１時間３０分、反応液を窒素気流下５０
Ｃに保ち、攪拌し続けた。次いで、減圧蒸留により、未
反応の塩化チオニルおよび副生物の二酸化硫黄を除去し
た後、反応液を５℃に冷却し、遠心分離によって反応生
成物である結晶を分取した。この結晶をジクロロエタン
で洗浄後、乾燥して白色の１−（２−クロロエチル）ピ
ペリジン塩酸塩１１９、０３ 、Ｆ （純度９９．５％
以上、透過率Ｔ４３０ｎｍ ＝ ９７４以上）を得た。Example 1 Thionyl chloride 80.2 g in dichloroethane 371.16 g
8.9 was dissolved to prepare a thionyl chloride solution. Separately,
Zokuooeta785.50. Dissolve 86.33 g of FKl-(2-hydroxyethyl)piperidine and dissolve 1-(2-hydroxyethyl)piperidine.
-Hydroxyethyl)pi(lysine solution was prepared.Next, under a nitrogen atmosphere, while stirring the thionyl chloride solution, the entire amount of the 1-(2-hydroxyethyl)piperidine solution was added to the thionyl chloride bath solution over 1 hour. After the dropwise addition, the reaction solution was heated for 50 minutes under a nitrogen stream for another 1 hour and 30 minutes.
C and continued stirring. Next, after removing unreacted thionyl chloride and by-product sulfur dioxide by distillation under reduced pressure, the reaction solution was cooled to 5° C., and the reaction product, crystals, was collected by centrifugation. The crystals were washed with dichloroethane and dried to give white 1-(2-chloroethyl)piperidine hydrochloride 119,03,F (purity 99.5%).
As described above, a transmittance T430nm = 974 or more) was obtained.
収率は、９６．８ ％であった。The yield was 96.8%.
実施例２
トルエン１５０．９に塩化チオニル７１．３８．９を溶
解し、塩化チオニル溶液を調製した。別にトルエン８０
．９に１−（２−ヒドロキシエチル）−４−メチルビペ
リノン７１．１１ｆＩを溶解し、１−（２−ヒドロキシ
エチル）−４−メチルピペリジン溶液を調製した。次に
、塩化チオニル溶液に１−（２−ヒドロキシエチル）−
４−メチルピペリジン溶液全量を３０分かけて滴下した
。滴下開始から反応終了まで温度を６０℃に保ち、授拌
し続けた。そして滴下後３０分で反応を終了した。次い
で未反応の塩化チオニルおよび副生物の二酸化硫黄を除
去した後、反応液を５℃に冷却して遠心分離を行い、反
応生成物である結晶を分取した。Example 2 A thionyl chloride solution was prepared by dissolving 71.38.9% of thionyl chloride in 150.9% of toluene. Separately, 80% toluene
．． 71.11 fI of 1-(2-hydroxyethyl)-4-methylbiperinone was dissolved in 9 to prepare a 1-(2-hydroxyethyl)-4-methylpiperidine solution. Next, add 1-(2-hydroxyethyl)- to thionyl chloride solution.
The entire amount of the 4-methylpiperidine solution was added dropwise over 30 minutes. The temperature was maintained at 60°C from the start of the dropwise addition to the end of the reaction, and stirring was continued. The reaction was completed 30 minutes after the dropwise addition. After removing unreacted thionyl chloride and by-product sulfur dioxide, the reaction solution was cooled to 5° C. and centrifuged to separate the reaction product, crystals.
この結晶をトールエンで洗浄後、乾燥して白色の１−（
２〜クロロエチル）−４−メチルピペリジン塩酸塩９３
．１４．９ （純度９９．０％以上、透過率Ｔ４３０ｎ
ｍ ＝９８’以上）を得た。収率は９５．５ ％でめっ
た。After washing the crystals with toluene and drying them, white 1-(
2-chloroethyl)-4-methylpiperidine hydrochloride 93
．． 14.9 (purity 99.0% or more, transmittance T430n
m = 98' or more) was obtained. The yield was 95.5%.
実施例３〜５
第１表に示す原料を使用して実施例１と同様に操作した
結果を第１表に示した。Examples 3 to 5 Table 1 shows the results of operations performed in the same manner as in Example 1 using the raw materials shown in Table 1.
比較例１
クロロホルムｌＱｍ／に塩化チオニル７．２ｇを溶かし
た溶液を水冷下１−（２−ヒドロキシエチル）ピペリシ
ン６、４６．９に３０分かけて滴下し、滴下終了後、さ
らに１，５時間、攪拌しなか、ら還流した。Comparative Example 1 A solution of 7.2 g of thionyl chloride dissolved in 1Qm/chloroform was added dropwise to 1-(2-hydroxyethyl)pipericine 6,46.9 over 30 minutes under water cooling, and after the completion of the dropwise addition, the solution was further added for 1.5 hours. The mixture was refluxed while stirring.
その後実施例１と同様に処理し、淡黄色の１−（２−ク
ロロエチル）ピペリノン塩酸塩８．６２．９（純度９７
．８％、透過率Ｔ４．ｏｎｍ＝ ６３．５ ％ ）を得
た。Thereafter, it was treated in the same manner as in Example 1, and pale yellow 1-(2-chloroethyl)piperinone hydrochloride 8.62.9% (purity 97%) was obtained.
．． 8%, transmittance T4. onm=63.5%) was obtained.
収率は、９３．６％であった。The yield was 93.6%.
Claims (6)
させることを特徴とする塩素化アミン塩酸塩の製造方法
。(1) A method for producing chlorinated amine hydrochloride, which comprises adding an amino alcohol to thionyl chloride and causing the reaction.
で希釈されたものであることを特徴とする特許請求の範
囲第（１）項記載の製造方法。(2) The production method according to claim (1), wherein thionyl chloride and the amino alcohol are diluted with an organic solvent.
基を示し、互いに同一でも異なっていてもよい。 また、ｍは１以上の整数である） で示される化合物である特許請求の範囲第（１）項記載
の製造方法。(3) Amino alcohol has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, R^1 and R^2 represent a hydrogen atom or an alkyl group, and may be the same or different from each other. (m is an integer of 1 or more) The method for producing the compound according to claim (1).
る） で示される化合物である特許請求の範囲第（１）項記載
の製造方法。(4) Claims in which the amino alcohol is a compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein n is 4 or 5, and m is an integer of 1 or more) The manufacturing method described in paragraph (1).
とする特許請求の範囲第（１）項の製造方法。(5) The manufacturing method according to claim (1), characterized in that the amino alcohol is added dropwise.
．８〜１．０モル添加することを特徴とする特許請求の
範囲第（１）項記載の製造方法。(6) 0 amino alcohol per mole of thionyl chloride
．． The manufacturing method according to claim (1), characterized in that 8 to 1.0 mol is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15485288A JPH0272142A (en) | 1988-06-24 | 1988-06-24 | Production of chlorinated amine hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15485288A JPH0272142A (en) | 1988-06-24 | 1988-06-24 | Production of chlorinated amine hydrochloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0272142A true JPH0272142A (en) | 1990-03-12 |
Family
ID=15593314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15485288A Pending JPH0272142A (en) | 1988-06-24 | 1988-06-24 | Production of chlorinated amine hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0272142A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557960A (en) * | 2010-12-28 | 2012-07-11 | 苏州飞翔新材料研究院有限公司 | Method for producing alkyl alcohol amine |
-
1988
- 1988-06-24 JP JP15485288A patent/JPH0272142A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557960A (en) * | 2010-12-28 | 2012-07-11 | 苏州飞翔新材料研究院有限公司 | Method for producing alkyl alcohol amine |
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