JPS6354340A - Production of chloroalkylamine hydrochlorides - Google Patents
Production of chloroalkylamine hydrochloridesInfo
- Publication number
- JPS6354340A JPS6354340A JP19649386A JP19649386A JPS6354340A JP S6354340 A JPS6354340 A JP S6354340A JP 19649386 A JP19649386 A JP 19649386A JP 19649386 A JP19649386 A JP 19649386A JP S6354340 A JPS6354340 A JP S6354340A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hydrochloride
- chloroalkylamine
- alkanolamine
- hydrochlorides
- 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
- 150000003840 hydrochlorides Chemical class 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- 238000005660 chlorination reaction Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 238000007281 aminoalkylation reaction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 7
- 239000002023 wood Substances 0.000 description 6
- FJIWMIJOXISTKW-UHFFFAOYSA-N 1-chloro-N-ethylpropan-2-amine hydrochloride Chemical compound Cl.C(C)NC(CCl)C FJIWMIJOXISTKW-UHFFFAOYSA-N 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SGBGCXQCQVUHNE-UHFFFAOYSA-N 2-(ethylamino)propan-1-ol Chemical compound CCNC(C)CO SGBGCXQCQVUHNE-UHFFFAOYSA-N 0.000 description 3
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FGSHJLJPYBUBHO-UHFFFAOYSA-N 2-chloroethyl(methyl)azanium;chloride Chemical compound [Cl-].C[NH2+]CCCl FGSHJLJPYBUBHO-UHFFFAOYSA-N 0.000 description 2
- VSBDRUDRPGMLHR-UHFFFAOYSA-N 2-chloropropylazanium;chloride Chemical compound Cl.CC(Cl)CN VSBDRUDRPGMLHR-UHFFFAOYSA-N 0.000 description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- 229940127557 pharmaceutical product Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JPGZDACJIPHKML-UHFFFAOYSA-N 2-aminopentan-3-ol Chemical compound CCC(O)C(C)N JPGZDACJIPHKML-UHFFFAOYSA-N 0.000 description 1
- WQMAANNAZKNUDL-UHFFFAOYSA-N 2-dimethylaminoethyl chloride Chemical compound CN(C)CCCl WQMAANNAZKNUDL-UHFFFAOYSA-N 0.000 description 1
- XIQMOJPBTZCSDM-UHFFFAOYSA-N 3-(dimethylamino)-2,3-dimethylbutan-2-ol Chemical compound CN(C)C(C)(C)C(C)(C)O XIQMOJPBTZCSDM-UHFFFAOYSA-N 0.000 description 1
- OVKDLPZRDQTOJW-UHFFFAOYSA-N 3-amino-2-methylbutan-2-ol Chemical compound CC(N)C(C)(C)O OVKDLPZRDQTOJW-UHFFFAOYSA-N 0.000 description 1
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 1
- BZFKSWOGZQMOMO-UHFFFAOYSA-N 3-chloropropan-1-amine Chemical compound NCCCCl BZFKSWOGZQMOMO-UHFFFAOYSA-N 0.000 description 1
- NTZBBKXYBTYXIC-UHFFFAOYSA-N 4-(dimethylamino)pentan-2-ol Chemical compound CC(O)CC(C)N(C)C NTZBBKXYBTYXIC-UHFFFAOYSA-N 0.000 description 1
- QTPSYGSRXIMHAH-UHFFFAOYSA-N CC(CC(C)Cl)N(C)C.Cl Chemical compound CC(CC(C)Cl)N(C)C.Cl QTPSYGSRXIMHAH-UHFFFAOYSA-N 0.000 description 1
- PNYHVDJFKBRIFJ-UHFFFAOYSA-N Cl.C(C)C(C(N)C)Cl Chemical compound Cl.C(C)C(C(N)C)Cl PNYHVDJFKBRIFJ-UHFFFAOYSA-N 0.000 description 1
- UBILXJUTXBOMHE-UHFFFAOYSA-N Cl.CN(CC(C(C)(C)Cl)(C)C)C Chemical compound Cl.CN(CC(C(C)(C)Cl)(C)C)C UBILXJUTXBOMHE-UHFFFAOYSA-N 0.000 description 1
- JSOHZEFFRHOGLB-UHFFFAOYSA-N Cl.NC(C(C)Cl)C Chemical compound Cl.NC(C(C)Cl)C JSOHZEFFRHOGLB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 206010061926 Purulence Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 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）
未発ＩＪＩはクロロアルキルアミン塩酸塩類を製造する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) Undeveloped IJI relates to a process for producing chloroalkylamine hydrochlorides.
（従来の技術）
クロロアルキルアミン塩酸塩類は、アミノアルキル化剤
として、農・医薬、染・顔料その他、各種工業薬品の中
間体や高分子化合物の原料として、極めて有用な物質で
ある。(Prior Art) Chloroalkylamine hydrochlorides are extremely useful substances as aminoalkylating agents, intermediates for agricultural and pharmaceutical products, dyes and pigments, and various other industrial chemicals, and raw materials for polymeric compounds.
クロロアルキルアミン塩酸塩類の製造方法はいくつか知
られているが有害ガスの発生あるいは品質的に熱変色す
るなど問題があった。そこで未発１１者らは特開昭５７
−１７６９３３号において高純度、高品質のクロロアル
キルアミン塩酸塩類を得るために、４０（ニル％以上の
クロロアルキルアミン塩酸塩と６０モル％以下のアルカ
ノールアミン１１！酸塩となるようにクロル化し除水し
たのち、さらに乾燥塩化水素を用いて２０ ｋｇ／ｃｒ
ｌＩ′Ｇ以下でクロル化する方法を提案した。この方法
によれば不純物の副生を抑制し品質的にも純度的にも極
めてよいクロロアルキルアミン１１！酸塩を得ることが
てきた。Several methods for producing chloroalkylamine hydrochlorides are known, but they have problems such as generation of harmful gases and thermal discoloration. There, the 11 unexploded individuals
In order to obtain high-purity, high-quality chloroalkylamine hydrochlorides in No. 176933, chlorination was carried out to obtain chloroalkylamine hydrochloride of 40% or more and alkanolamine 11! of 60% or less by mole. After watering, add dry hydrogen chloride to 20 kg/cr.
We proposed a method for chlorination below lI'G. According to this method, the by-product of impurities is suppressed and the chloroalkylamine 11 is extremely good in terms of quality and purity! I have been able to obtain acid salts.
（発明が解決しようとする問題点）
しかし、」二足特開昭５７−１７６９３３号記伎の方法
では反応系内は生成する水により塩酸系となるため、反
応器は耐食材を用いな４１ればならない。このような耐
食材としてタンタル、グラスライニング等が考えられる
かコスト的には通常ではグラスライニング材を選択する
ことが一般的である。グラスライニング材を用いる場合
、反応規模が小さければ常用圧力１０ ｋｇ／ｃｍ’Ｇ
、 ２０ｋｇ／ｃｒｎ’Ｇの反応器を製作することに
何ら問題はないが、たとえば内容琶２０ｍ′の反応器の
場合常用圧力１０ ｋｇ／ｃｒｎ”Ｇては反応器母材の
厚みが数１０１となりグラスライニング反応器製作上に
問題が生じる。したかって実質的に製作可濠な範囲は常
用圧カフ ｋｇ／ ｃｍ’ Ｇか限度になる。このよう
に反応圧力は反応器容量からの制限を受け、それ故低圧
下て合成てきる方法の開発が要望されている。(Problems to be Solved by the Invention) However, in the method described in Japanese Patent Application Laid-Open No. 57-176933, the reaction system becomes hydrochloric acid-based due to the water produced, so the reactor must not be made of corrosion-resistant material. Must be. Tantalum, glass lining, etc. are conceivable as such corrosion-resistant material, but glass lining materials are usually selected from a cost standpoint. When using glass lining material, if the reaction scale is small, the normal pressure is 10 kg/cm'G.
There is no problem in manufacturing a reactor with a capacity of 20 kg/crn'G, but for example, in the case of a reactor with a capacity of 20 m', if the normal pressure is 10 kg/crn'G, the thickness of the reactor base material will be several 101. A problem arises when manufacturing a glass-lined reactor.Therefore, the range that can be practically manufactured is limited to the normal pressure cuff kg/cm'G.In this way, the reaction pressure is limited by the reactor capacity. Therefore, there is a demand for the development of a method for synthesis under low pressure.
また、クロロアルキルアミン塩酸塩類は医薬品の原料と
なることから副生成物はもとより未反応原料であるアル
カノールアミン塩酸塩をも含まないような極めて高品質
、高純度の製品を要求される。ところが従来１本発ｌＪ
】者らか特開昭５７−１７６９３３号で提案した方法で
単に反応圧力を下げると純度か低下する傾向にあった。In addition, since chloroalkylamine hydrochlorides are used as raw materials for pharmaceutical products, products of extremely high quality and purity are required that do not contain by-products or even alkanolamine hydrochloride, which is an unreacted raw material. However, conventionally one-shot lJ
] If the reaction pressure was simply lowered using the method proposed by them in JP-A-57-176933, the purity tended to decrease.
加えて、クロル化反応を２回に分けて、かつ、その間て
反応系内からの水分の分離を目的とした濃縮を行うため
１反応時間のロスとなるなど経済性の面からも欠点かあ
った。In addition, since the chlorination reaction is divided into two steps and concentration is performed in between to separate water from the reaction system, one reaction time is lost, which has some drawbacks from an economic standpoint. Ta.
（問題点を解決するための手段）
本発明者らは上記従来法の欠点を克服するため鋭意研究
を重ねた結果アルカノールアミン塩酸塩に乾燥塩化水素
を作用させて塩素化を行なう場合、
■反応の進行に伴ない生成する木が逆反応すなわち生成
したクロロアルキルアミン塩酸塩かアルカノールアミン
塩酸塩に戻る反応を促進させること、
■反応系の塩酸濃度を高めることにより生成水の影響を
減少させこの逆反応を抑制できること、
などの知見を得た。そしてこれらに加えて乾燥塩化水素
を用い、かつ、低圧力下ても反応温度を下げることによ
り反応系での塩酸濃度を高め、かつ、アルカノールアミ
ン塩酸塩類中の含水率を制御するという手段を採用する
ことにより低圧合成条件下で、かつ、−度のクロル化反
応でも高純度（例えばクロロアルキルアミン塩酸塩の純
度が９８．５〜９９．９重量％の範囲）のクロロアルキ
ルアミン塩酸塩を得ることを見い出した。(Means for Solving the Problems) The present inventors have conducted extensive research to overcome the drawbacks of the conventional methods described above, and as a result, when chlorinating alkanolamine hydrochloride with dry hydrogen chloride, To promote the reverse reaction of the wood produced as the process progresses, that is, to return to the produced chloroalkylamine hydrochloride or alkanolamine hydrochloride, and to reduce the influence of the produced water by increasing the hydrochloric acid concentration in the reaction system. We obtained findings such as that reverse reactions can be suppressed. In addition to these methods, we adopted a method of increasing the concentration of hydrochloric acid in the reaction system by using dry hydrogen chloride and lowering the reaction temperature even under low pressure, and controlling the water content in alkanolamine hydrochlorides. By doing so, chloroalkylamine hydrochloride of high purity (for example, the purity of chloroalkylamine hydrochloride ranges from 98.5 to 99.9% by weight) is obtained under low-pressure synthesis conditions and even in a -degree chlorination reaction. I discovered that.
すなわち未発ＩＪＪは、一般式（Ｉ）
（式中、Ｒ、Ｒ、ＲおよびＲ４は水素原子または低級ア
ルキル基を示し、互いに同一でも異なっていてもよい、
またｎは２〜４の整数を意味する。このとき、各炭素原
子に結合するＲ３、Ｒ４は互いに同一でも異なっていて
もよい）で表わされるアルカノールアミン類をクロル化
して、一般式（ｎ）
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびｎは前記と同じ
意味をもつ、）
で表わされるクロロアルキルアミン塩酸塩類を製造する
方法において、３ 、０〜７ 、０ ｋｇ／ｃｍ’Ｇの
圧力で含水率３．０重量％以下のアルカノールアミン塩
酸ｍと乾燥塩化水素とを１００〜１４０℃て反応させる
ことを特徴とするクロロアルキルアミン塩酸塩類の製造
方法を提供するものである。That is, undeveloped IJJ has the general formula (I) (wherein R, R, R and R4 represent a hydrogen atom or a lower alkyl group, and may be the same or different from each other,
Moreover, n means an integer of 2 to 4. At this time, the alkanolamines represented by the general formula (n) (wherein R1, R2, R3, R4 and In the method for producing chloroalkylamine hydrochlorides represented by (n has the same meaning as above), an alkanolamine having a water content of 3.0% by weight or less at a pressure of 3,0 to 7,0 kg/cm'G. The present invention provides a method for producing chloroalkylamine hydrochlorides, which comprises reacting hydrochloric acid m with dry hydrogen chloride at 100 to 140°C.
以下、本発明の詳細な説１５１する。A detailed explanation of the present invention will be given below.
本発明におけるアルカノールアミン類の塩化水素による
クロル化反応は次式に従って進行すると考えられる。The chlorination reaction of alkanolamines with hydrogen chloride in the present invention is thought to proceed according to the following formula.
（Ｉ） （Ｉ） （ＩＩ） すなわち、総括的には次のように表わすことができる。(I) (I) (II) That is, it can be generally expressed as follows.
（Ｉ）
（ＩＩ）
（上記（Ｉ）、（■）′、（ｎ）式中Ｒ１、Ｒ、Ｒ、お
よびＲ４は水素原子または低級アルキル基を示し、互い
に同一でも異なっていてもよい。またｎは２−４の整数
を意味する。このとき各炭素原子に付＜Ｒ３，Ｒ４は互
いに同一でも異なっていてもよい）
（３）式より明らかなように、クロロアルキルアミン塩
酸塩類（ＩＩ）が１モル生成することに木か１モル副生
ずる。(I) (II) (In the above formulas (I), (■)', and (n), R1, R, R, and R4 represent a hydrogen atom or a lower alkyl group, and may be the same or different from each other. n means an integer of 2-4. In this case, <R3 and R4 attached to each carbon atom may be the same or different from each other.) As is clear from the formula (3), chloroalkylamine hydrochloride (II) For every 1 mol of wood produced, 1 mol of wood is produced as a by-product.
本発明において反応原料として使用するアルカノールア
ミン類は上記（３）式中一般式（Ｉ）で表わされる化合
物で、たとえば２−アミノエタノール、２−ジメチルア
ミノエタノール、２−エチルアミノ−プロパノール、ｌ
−メチル−２−アミノエタノール、１−エチル−２−メ
チル−２−アミノエタノール、１．１−ジメチル−２−
メチル−２−アミノエタノール、１，１，２．２−テト
ラメチル−２−ジメチルアミノエタノール、３−アミノ
−１−プロパツール、３−ジメチルアミツブロバノール
、２−アミノ−１−メチル−１−プロパツール、１−ア
ミノ−２−プロパツール、３−ジメチルアミノ−１，１
，２，２−テトラメチル−１−プロパツール、４−アミ
ノ−１−ブタノール、３−ジメチルアミノ−１−メチル
−１−ブタノールなどがある。The alkanolamines used as reaction raw materials in the present invention are compounds represented by the general formula (I) in the above formula (3), such as 2-aminoethanol, 2-dimethylaminoethanol, 2-ethylamino-propanol, l
-Methyl-2-aminoethanol, 1-ethyl-2-methyl-2-aminoethanol, 1,1-dimethyl-2-
Methyl-2-aminoethanol, 1,1,2.2-tetramethyl-2-dimethylaminoethanol, 3-amino-1-propatol, 3-dimethylamitubrobanol, 2-amino-1-methyl-1 -Propatur, 1-amino-2-propatur, 3-dimethylamino-1,1
, 2,2-tetramethyl-1-propatol, 4-amino-1-butanol, 3-dimethylamino-1-methyl-1-butanol, and the like.
また、本発明により得られるクロロアルキルアミン塩酸
塩類は上記（３）式中一般式（ＩＩ）て表わされる化合
物で、たとえば、２−クロロエチルアミン塩酸塩、２−
ジメチルアミノエチルクロリト１１！酸塩、２−エチル
アミノ−１−プロとルクロリ１〜塩酸用、１−メチル−
２−アミノエチルクロリド塩酸塩、１−エチル−２−メ
チル−２−アミノエチルクロリド塩酸塩、１．１−ジメ
チル−２−メチル−２−アミノエチルクロリド塩酸塩、
１．１，２．２−テトラメチル−２−ジメチルアミノエ
チルクロリド塩酸塩、３−アミノ−１−プロピルクロリ
ドＩＩＸＭ塩、３−ジメチルアミノ−１−プロピルクロ
リド塩酸塩、２−アミノ−１−メチル−１−プロピルク
ロリド塩酸塩、ｌ−アミノ−２−プロピルクロリド塩酸
塩、３−ジメチルアミノ−１，ｌ、２．２−テトラメチ
ル−１−プロピルクロリド塩酸１，４−アミノ−１−ブ
チルクロリド塩酸塩、３−ジメチルアミノ−１−メチル
−１−ブチルクロリド塩酸塩などがある。In addition, the chloroalkylamine hydrochlorides obtained by the present invention are compounds represented by the general formula (II) in the above formula (3), such as 2-chloroethylamine hydrochloride, 2-
Dimethylaminoethyl chloride 11! Acid acid, 2-ethylamino-1-pro and chloride 1-for hydrochloric acid, 1-methyl-
2-aminoethyl chloride hydrochloride, 1-ethyl-2-methyl-2-aminoethyl chloride hydrochloride, 1.1-dimethyl-2-methyl-2-aminoethyl chloride hydrochloride,
1.1,2.2-Tetramethyl-2-dimethylaminoethyl chloride hydrochloride, 3-amino-1-propyl chloride IIXM salt, 3-dimethylamino-1-propyl chloride hydrochloride, 2-amino-1-methyl -1-Propyl chloride hydrochloride, 1-amino-2-propyl chloride hydrochloride, 3-dimethylamino-1,1,2,2-tetramethyl-1-propyl chloride hydrochloride 1,4-amino-1-butyl chloride Hydrochloride, 3-dimethylamino-1-methyl-1-butyl chloride hydrochloride, etc.
本発明の反応は式（３）に示したごとく、脱水クロル化
反応であり、かつ、反応系内に存在する水によって化学
平衡か存在する。従って水の影響を少しても減少させる
ため本発明においては、含水率か３６０重量％以下のカ
ルカノールアミン塩酸塩類と、乾燥塩化水素とを反応さ
せるにあたり、反応温度１００〜１４０℃の範囲とする
。As shown in formula (3), the reaction of the present invention is a dehydration chlorination reaction, and a chemical equilibrium exists due to the water present in the reaction system. Therefore, in order to reduce the influence of water as much as possible, in the present invention, when reacting carkanolamine hydrochloride with a water content of 360% by weight or less and dry hydrogen chloride, the reaction temperature is set in the range of 100 to 140°C. .
この場合、反応前半の反応温度をより高く、後半をより
低くするのが好ましく、これによってさらに純度を向上
させることかてきる。In this case, it is preferable to set the reaction temperature higher in the first half of the reaction and lower in the second half, thereby further improving the purity.
もし、上記の含水率３．０重量％以」二残存したアルカ
ノールアミン塩酸塩類を乾燥塩化水素と反応させた場合
反応によって生成する水との相加によって、高純度のク
ロロアルキルアミン塩酸塩は得られない、これに反して
高純度のクロロアルキルアミン塩酸塩を得るには、反応
圧力を極端に高くし、反応液中の塩酸濃を高める必要か
生ずる。If the remaining alkanolamine hydrochloride with a moisture content of 3.0% by weight or more is reacted with dry hydrogen chloride, high-purity chloroalkylamine hydrochloride can be obtained by addition with the water produced by the reaction. On the other hand, in order to obtain highly pure chloroalkylamine hydrochloride, it is necessary to extremely increase the reaction pressure and increase the concentration of hydrochloric acid in the reaction solution.
しかし、前述の如く反応器製作上の問題点かクローズア
ップされ、工業的に大容量ての生産か困難となる。However, as mentioned above, problems in reactor manufacturing have been highlighted, making it difficult to produce large-capacity industrially.
これに対してアルカノールアミン塩酸塩の含水率を３．
０重量％以下、好ましくは１．０重量％以下、さらに好
ましくは０．３重量％、最も好ましくは０．１重量％以
下にし、さらにクロル化の温度条件をコントロールする
ことにより高純度すなわち純度９８〜９９．９重琶％の
クロロアルキルアミン塩酸塩を得ることか可能となる。In contrast, the water content of alkanolamine hydrochloride was 3.
By controlling the temperature to 0% by weight or less, preferably 1.0% by weight or less, more preferably 0.3% by weight, most preferably 0.1% by weight or less, and controlling the temperature conditions of chlorination, high purity, i.e., purity 98% can be obtained. It becomes possible to obtain chloroalkylamine hydrochloride of ~99.9% by weight.
クロル化反応の′＃Ａ度については、１００℃未満の温
度では反応速度が非常に遅く、反応の完結に多大な時間
を要し実用的でない、また反応温度が１４０℃を越える
と反応速度は速くなる反面１反応系の着色が極めて大き
く、かつ、熱分解により逆に目的物の収率や純度の低下
を招くこと、および装を材質の観点からしても反応温度
が１４０℃を越えると塩化水素酸に対し長期間耐え得る
安価な材料がないので上限としては１４０℃か採用され
る。Regarding the A degree of chlorination reaction, if the temperature is less than 100°C, the reaction rate is very slow and it takes a long time to complete the reaction, which is not practical.If the reaction temperature exceeds 140°C, the reaction rate is too slow. On the other hand, the coloring of the reaction system is extremely large, and thermal decomposition causes a decrease in the yield and purity of the target product.Also, from the viewpoint of the material used for the packaging, if the reaction temperature exceeds 140℃, Since there is no inexpensive material that can withstand hydrochloric acid for a long period of time, an upper limit of 140° C. is adopted.
本反応は前述のごとく高温はど反応は速いが反応が進む
につれ特に未反応アルカノールアミン塩酸塩類の組成が
１０モル％以下になってくると反応系内の水の影響を受
は進行しづらくなる。この時点で反応液中のＪＵＭ膿度
を高めることにより。As mentioned above, this reaction is fast at high temperatures, but as the reaction progresses, especially when the composition of unreacted alkanolamine hydrochloride becomes less than 10 mol%, it becomes difficult to proceed due to the influence of water in the reaction system. . By increasing the JUM purulence in the reaction solution at this point.
水の影響を弱め再び反応が進行しはじめる。すなわち、
クロル化反応の前半は反応温度を高めに設定することに
より反応時間を短かくし、後半は反応液中の塩酸濃度を
高めることによりクロロアルキルアミン塩酸塩類の生成
率を］」標値迄向上させるのが好ましい、ここで述べた
反応系の塩酸の濃度をあげるには一般的には圧力を上げ
る方法が採用される。しかし本反応は圧力が固定される
ためそれにかわる方法として温度を下げることにより目
的を達成する。The effect of water is weakened and the reaction begins to proceed again. That is,
In the first half of the chlorination reaction, the reaction time is shortened by setting the reaction temperature higher, and in the second half, the production rate of chloroalkylamine hydrochlorides is improved to the target value by increasing the concentration of hydrochloric acid in the reaction solution. is preferred.To increase the concentration of hydrochloric acid in the reaction system described here, a method of increasing the pressure is generally adopted. However, since the pressure is fixed in this reaction, the objective can be achieved by lowering the temperature instead.
温度の下げ方については反応初期から連続的に下げても
数度ごと段階的に下げてもかまわない。Regarding the method of lowering the temperature, it may be lowered continuously from the initial stage of the reaction or it may be lowered stepwise in steps of several degrees.
反応時間の短縮および操作性を考慮するとクロル化反応
の前半を１２０〜１４０℃、好ましくは１２５〜１３５
℃１より好ましくは１３０℃で行ない後半を１００〜１
２０℃、好ましくは１０５〜１１５℃１より好ましくは
１１０℃て行なうことにより前述の、純度９８〜９９．
９重量％のクロルアルキルアミン塩酸塩を得ることがで
きる。Considering shortening of reaction time and operability, the first half of the chlorination reaction is carried out at 120 to 140°C, preferably 125 to 135°C.
The temperature is preferably 130℃ rather than ℃1, and the second half is heated to 100-1℃.
The above-mentioned purity of 98-99.
9% by weight of chloralkylamine hydrochloride can be obtained.
る。Ru.
未発ＩＪ１ニおける反応圧力は３〜７ ｋｇ／ｃｍ’
Ｇ 。The reaction pressure at unreleased IJ1 is 3-7 kg/cm'
G.
好ましくは４〜７ ｋｇ／ｃｒｎ’Ｇ 、より好ましく
は、４ 、５〜７ ｋｇ／ｃｍ’ Ｇか採用される。Preferably 4 to 7 kg/cm'G, more preferably 4 or 5 to 7 kg/cm'G is employed.
本発明において反応圧力は反応液中に塩化水素か溶解し
アルカノールアミン塩酸塩類との接触効率を上げること
かつ、反応液中の塩酸濃度を高め木の影響を弱めるため
にも高圧であることが望ましい、しかし、反応器の容量
によって反応器の設訂圧力は前述のごとく反応器製作上
の理由で制限されるため最大７ｋｇ／ｃｍ’Ｇとする。In the present invention, the reaction pressure is preferably high in order to dissolve hydrogen chloride in the reaction solution and increase the contact efficiency with the alkanolamine hydrochloride, and also to increase the concentration of hydrochloric acid in the reaction solution and weaken the effect of wood. However, the set pressure of the reactor is limited by the capacity of the reactor due to reactor manufacturing reasons, as described above, so it is set to a maximum of 7 kg/cm'G.
将来反応器の製作」二、さらに高圧が可ずＬであれば必
要に応じて反応圧力をさらに高めてもよい、また３ｋｇ
／ｃｍ”Ｇ未満では反応系内のＪ′！！酸濃度が低く反
応を十分に進めることかできない。2. If higher pressure is not possible, the reaction pressure may be further increased as necessary, and 3 kg.
/cm''G, the concentration of J'!! acid in the reaction system is so low that the reaction cannot proceed sufficiently.
原料となるアルカノールアミン塩酸塩類を用意するにあ
たって、アルカノールアミン類と塩酸とを中和して得て
もよく、また、乾燥塩化水粱を作用させて得てもよい、
この中和反応時発熱を伴ない、高温ではアルカノールア
ミン類が熱変質をおこすため低温で、望ましくは５０℃
以下で中和する。また上述のアルカノールアミン塩酸塩
に木が含まれている場合濃縮脱水を行うが、この除水方
法は特に制限はないか、ｉｉｏ’ｃ以下、３０■ｓｉＨ
ｇ以下で減圧濃縮すると目標とする含水率か得られる。In preparing the alkanolamine hydrochloride as a raw material, it may be obtained by neutralizing the alkanolamine and hydrochloric acid, or it may be obtained by reacting with dried chloride starch.
This neutralization reaction is accompanied by heat generation, and alkanolamines undergo thermal deterioration at high temperatures, so it is preferable to use a low temperature, preferably 50℃.
Neutralize with: In addition, if the above-mentioned alkanolamine hydrochloride contains wood, concentration dehydration is performed, but is there any particular restriction on this water removal method?
The target moisture content can be obtained by concentrating under reduced pressure at less than 100 g.
濃縮温度がｉｉｏ’ｅを越えると着色か生じやすくなる
。When the concentration temperature exceeds io'e, coloring tends to occur.
未発ＩＪＩにおける反応操作は具体的にはたとえば以下
のごとくして行なわれる。Specifically, the reaction operation in undeveloped IJI is carried out, for example, as follows.
まず（１）式による中和反応を行う。すなわち、アルカ
ノールアミン類１モルを１モル以上のＣ塩酸（３６ｗｔ
％）中に添加すると中和反応（発熱）のため急激な温度
上昇を来たすので、これを防止するため添加速度を調節
しながら徐々に温度を上げていく。First, a neutralization reaction according to equation (1) is performed. That is, 1 mol of alkanolamines is mixed with 1 mol or more of C hydrochloric acid (36wt
%), the temperature will rise rapidly due to the neutralization reaction (heat generation), so to prevent this, the temperature is gradually raised while adjusting the addition rate.
通常反応温度は、アルカノールアミンの熱変質を考慮し
５０″Ｃ以内が望ましい。中和反応か終了した後加熱し
、Ｚｏｏ℃以内で減圧濃縮し、反応系の水分を０．５重
量％以下にする。減圧澁縮終了後、反応器を減圧に保持
したまま加熱し１１０℃とした時点で塩化水素の供給を
開始し連続的に供給をつづけ反応によって発生する熱と
加熱とで１３０℃迄上昇させ温度制御を行なう、また反
応圧力は圧力調整機で所定の圧力に設定し制御する。Usually, the reaction temperature is preferably within 50"C in consideration of thermal deterioration of the alkanolamine. After the neutralization reaction is completed, it is heated and concentrated under reduced pressure within ZooC to reduce the water content of the reaction system to 0.5% by weight or less. After the completion of the vacuum condensation, the reactor was heated while maintaining the vacuum, and when the temperature reached 110°C, the supply of hydrogen chloride was started and the supply was continued until the temperature rose to 130°C due to the heat generated by the reaction and the heating. The reaction pressure is controlled by setting it to a predetermined pressure using a pressure regulator.
アルカノールアミン塩酸塩からクロロアルキルアミン塩
酸塩への転化が極端に遅くなった時点で反応温度を１１
０℃迄下げ反応なａ続させる。その後この反応系から木
および過剰の塩化水素３０ａｍ！ｔｇ以下、１１０℃以
下でＣ縮乾固することにより精製処理を施すことなく直
接高純度のクロロアルキルアミン塩酸塩類を得ることが
できる。When the conversion of alkanolamine hydrochloride to chloroalkylamine hydrochloride becomes extremely slow, the reaction temperature is increased to 11
Continue the reaction by lowering the temperature to 0°C. This reaction system then contains wood and 30 am of excess hydrogen chloride! High purity chloroalkylamine hydrochlorides can be obtained directly without purification by condensation to dryness at a temperature below tg and below 110°C.
（発明の効果）
本発明によれば不純物の副生を抑制し、高品質、高純度
のクロロアルキルアミン塩酸塩を製造することができる
。(Effects of the Invention) According to the present invention, it is possible to suppress the by-product of impurities and to produce a high-quality, high-purity chloroalkylamine hydrochloride.
本発明方法によれば、低圧力条件で高純度のクロロアル
キルアミン塩酸塩を製造でき１反応のスケールアップに
より、工業的に大容量での生産かできる。According to the method of the present invention, highly pure chloroalkylamine hydrochloride can be produced under low pressure conditions, and by scaling up one reaction, it can be produced industrially in large quantities.
（実施例）
以下、実施例により未発［Ｊｌをより具体的に説明する
がこれらは単なる例示であり、未発Ｉ」がこれら実施例
に限定されるものでないことはもちろんである。(Examples) Hereinafter, the unreleased Jl will be explained in more detail with reference to examples, but these are merely examples, and it goes without saying that the unreleased I is not limited to these examples.
実施例１
攪拌機、湿度制御装置、圧力制御装置を備えた５ｏｏＴ
ｒ？、グラスオートクレーブに３６％塩酸（塩化水素と
して２．１モル相当）を仕込み攪拌下に２−アミノエタ
ノール１２２ｇを５０℃以下で中和するように滴下した
。中和反応が終了した時点で加熱を開始し、つづいて減
圧ｉｅ縮を開始し、真空度２１ ｍ＊＋Ｈｇ、温度９８
℃となったところて脱水を終了した。このときの反応系
の水分は０．６重量％であった。Example 1 5ooT equipped with a stirrer, humidity control device, and pressure control device
r? A glass autoclave was charged with 36% hydrochloric acid (corresponding to 2.1 moles of hydrogen chloride), and 122 g of 2-aminoethanol was added dropwise to the autoclave with stirring to neutralize the mixture at 50° C. or below. When the neutralization reaction was completed, heating was started, followed by reduced pressure ie condensation, and the vacuum was 21 m*+Hg and the temperature was 98.
Dehydration was completed when the temperature reached ℃. The water content of the reaction system at this time was 0.6% by weight.
この系を再び減圧にしたあと、乾燥塩化水素を供給する
とともに加熱を開始し、１３０℃、５ 、５ ｋｇ／ｃ
ｒｎ’Ｇで制御した。塩化水素の供給開始後、２４蒔間
でクロルエチルアミン塩酸塩の純度は９７．７重量％で
あった０反応器度をその後１１Ｏ℃に下げ、１２時間反
応させたところ、純度は９８．９重量％となった。After reducing the pressure in this system again, dry hydrogen chloride was supplied and heating was started, at 130°C, 5.5 kg/c.
Controlled with rn'G. After starting the supply of hydrogen chloride, the purity of chloroethylamine hydrochloride was 97.7% by weight after 24 minutes.The temperature of the reactor was then lowered to 110°C and the reaction was continued for 12 hours, and the purity was 98.9% by weight. %.
実施例２
反応圧力を３．５ｋｇ／ｅゴＧに変更し、かつ、原料を
４−アミノ−１−ブタノールに変更した以外は実施例１
と同様の方法で合成したところ得られた４−アミノ−１
−ブチルクロリド塩酸塩の純度は９８．２重量％であっ
た。Example 2 Example 1 except that the reaction pressure was changed to 3.5 kg/eG and the raw material was changed to 4-amino-1-butanol.
4-Amino-1 obtained by synthesis in the same manner as
The purity of -butyl chloride hydrochloride was 98.2% by weight.
実施例３
反応圧カフ、０ｋｇ／ｃゴＧに変更し、また原料を２−
メチルアミノエタノールに変更した以外は実施例１と同
様の方法で合成したところ、２−メチルアミノエチルク
ロリド塩酸塩の純度は９９．２重量％であった。Example 3 The reaction pressure cuff was changed to 0 kg/c GoG, and the raw material was changed to 2-
Synthesis was performed in the same manner as in Example 1 except that methylaminoethanol was used, and the purity of 2-methylaminoethyl chloride hydrochloride was 99.2% by weight.
比較例１
含水率７．２重量％の２−メチルアミノエタノールの塩
酸塩を原料として用い、反応圧力４ 、５ ｋｇ／ｃｒ
ｎ’Ｇとした以外は実施例１と同様の方法て合成した。Comparative Example 1 Hydrochloride of 2-methylaminoethanol with a water content of 7.2% by weight was used as a raw material, and the reaction pressure was 4.5 kg/cr.
It was synthesized in the same manner as in Example 1 except that n'G was used.
その結果、２−メチルアミノエチルクロリド塩酸塩の純
度は９２．４１ｉＸ量％であった。As a result, the purity of 2-methylaminoethyl chloride hydrochloride was 92.41 iX% by weight.
実施例４
含）ＫＨｌ、 ３ 、 ｌ ｇＩ 量％の２−エチル
アミノ−プロパノールの塩酸塩を用いた以外はツ施例１
と同様の方法でクロル化を行ったところ２−エチルアミ
ノ−１−プロピルクロリド塩酸塩の純度は９８．２重量
％であった。Example 4 Example 1 except that the hydrochloride of 2-ethylamino-propanol was used in an amount of % KHl, 3, l gI
When chlorination was carried out in the same manner as above, the purity of 2-ethylamino-1-propyl chloride hydrochloride was 98.2% by weight.
比較例２
含水率１．８重量％の２−エチルアミツブロバノール塩
酸１１！を用い反応圧力を２ 、６ ｋｇ／ｅｒｎ’
Ｇに変更した以外は実施例１と同様の方法で合成したと
ころ、２−エチルアミノ−１−プロピルクロリド塩酸塩
の純度は９３．１玉量％であった。Comparative Example 2 2-ethylamitubrobanol hydrochloride 11 with a water content of 1.8% by weight! The reaction pressure was set to 2.6 kg/ern'
When synthesized in the same manner as in Example 1 except that G was used, the purity of 2-ethylamino-1-propyl chloride hydrochloride was 93.1% by weight.
実施例５
含水率１．４重量％の２−エチルアミツブロバノールの
塩酸塩を用い、反応圧力６ 、５ ｋｇ／ｃｒｎ’ Ｇ
とし、かつ、温度をはじめから１１０℃に下げた以外は
実施例１と全く同様にしてクロル化反応を行った。この
結果２−エチルアミノ−１−プロピルクロリド塩酸塩の
純度が９８．５重量％に達するのに反応時間７４時間を
要した。Example 5 Using 2-ethylamitublobanol hydrochloride with a water content of 1.4% by weight, the reaction pressure was 6.5 kg/crn'G.
A chlorination reaction was carried out in exactly the same manner as in Example 1, except that the temperature was lowered to 110°C from the beginning. As a result, it took a reaction time of 74 hours for the purity of 2-ethylamino-1-propyl chloride hydrochloride to reach 98.5% by weight.
実施例６
反応圧力を５ｋｇ／ｃｒｎ’Ｇとし、含水率０．３重量
％の２−エチルアミノ−プロパノールの塩酸塩と１３０
℃か６７時間毎に５℃きざみで反応温度を下げ、１１０
″Ｃに達してから７時間後に反応を停止させたところ得
られた２−エチルアミノプロピルクロリド塩酸塩の純度
は９９．５重輩％であった。Example 6 The reaction pressure was 5 kg/crn'G, and the hydrochloride of 2-ethylamino-propanol with a water content of 0.3% by weight was
Reduce the reaction temperature in 5°C increments every 67 hours to 110°C.
When the reaction was stopped 7 hours after reaching "C", the purity of 2-ethylaminopropyl chloride hydrochloride obtained was 99.5% by weight.
比較例３
反応温度をはじめから９０℃に固定した以外は、実施例
５と同様にして反応を１週間行わせたところ２−エチル
アミノプロピルクロリド塩酸塩の純度はａｉ、ｉ重量％
であった。Comparative Example 3 The reaction was carried out for one week in the same manner as in Example 5, except that the reaction temperature was fixed at 90°C from the beginning. The purity of 2-ethylaminopropyl chloride hydrochloride was ai, i% by weight.
Met.
実施例７
反応温度を１３０℃に固定し、温度を下げないようにし
た以外は実施例１と同様の方法で反応を行わせた。その
結果クロロエチルアミン塩酸塩の純度は９８，１重量％
であった。Example 7 A reaction was carried out in the same manner as in Example 1, except that the reaction temperature was fixed at 130°C and the temperature was not lowered. As a result, the purity of chloroethylamine hydrochloride was 98.1% by weight.
Met.
Claims (4)
子または低級アルキル基を示し、互いに同一でも異なっ
ていてもよい。またｎは２〜４の整数を意味する。この
とき、各炭素原子に結合するＲ＾３、Ｒ＾４は互いに同
一でも異なっていてもよい）で表わされるアルカノール
アミン類をクロル化して、一般式（II） ▲数式、化学式、表等があります▼ （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４およびｎは前
記と同じ意味をもつ。） で表わされるクロロアルキルアミン塩酸塩類を製造する
方法において、３．０〜７．０ｋｇ／ｃｍ＾２Ｇの圧力
で含水率３．０重量％以下のアルカノールアミン塩酸塩
と乾燥塩化水素とを１００〜１４０℃で反応させること
を特徴とするクロロアルキルアミン塩酸塩類の製造方法
。(1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3 and R^4 represent hydrogen atoms or lower alkyl groups, and they may be the same as each other. and n means an integer of 2 to 4. In this case, R^3 and R^4 bonded to each carbon atom may be the same or different from each other). is chlorinated to give the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, R^3, R^4 and n have the same meanings as above.) In the method for producing chloroalkylamine hydrochlorides represented by A method for producing chloroalkylamine hydrochlorides, characterized by carrying out the reaction at °C.
ルカノールアミン水溶液を塩酸で中和し減圧下に濃縮し
たものである特許請求の範囲第１項記載のクロロアルキ
ルアミン塩酸塩類の製造方法。(2) The method for producing chloroalkylamine hydrochlorides according to claim 1, wherein the alkanolamine hydrochloride used in the chlorination is obtained by neutralizing an alkanolamine aqueous solution with hydrochloric acid and concentrating it under reduced pressure.
ることを特徴とする特許請求の範囲第１項又は第２項記
載のクロロアルキルアミン塩酸塩類の製造方法。(3) The method for producing chloroalkylamine hydrochlorides according to claim 1 or 2, characterized in that the reaction temperature in the first half of the chlorination reaction is higher than in the second half.
また後半を反応温度１００〜１２０℃で行うことを特徴
とする特許請求の範囲第１項又は第２項記載のクロロア
ルキルアミン塩酸塩類の製造方法。(4) The reaction temperature for the first half of the chlorination reaction is 120-140℃
The method for producing chloroalkylamine hydrochlorides according to claim 1 or 2, wherein the latter half is carried out at a reaction temperature of 100 to 120°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196493A JP2657642B2 (en) | 1986-08-23 | 1986-08-23 | Method for producing chloroalkylamine hydrochlorides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61196493A JP2657642B2 (en) | 1986-08-23 | 1986-08-23 | Method for producing chloroalkylamine hydrochlorides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6354340A true JPS6354340A (en) | 1988-03-08 |
| JP2657642B2 JP2657642B2 (en) | 1997-09-24 |
Family
ID=16358688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61196493A Expired - Fee Related JP2657642B2 (en) | 1986-08-23 | 1986-08-23 | Method for producing chloroalkylamine hydrochlorides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2657642B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133247A (en) * | 1980-03-21 | 1981-10-19 | Teijin Ltd | Production of 2-chloroethylamine hydrochloride |
| JPS57176933A (en) * | 1981-04-24 | 1982-10-30 | Mitsui Toatsu Chem Inc | Improved method for preparation of chloroalkylamine hydrochloride |
-
1986
- 1986-08-23 JP JP61196493A patent/JP2657642B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133247A (en) * | 1980-03-21 | 1981-10-19 | Teijin Ltd | Production of 2-chloroethylamine hydrochloride |
| JPS57176933A (en) * | 1981-04-24 | 1982-10-30 | Mitsui Toatsu Chem Inc | Improved method for preparation of chloroalkylamine hydrochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2657642B2 (en) | 1997-09-24 |
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