JPH0324039A - Production of trimethylamine-sulfur trioxide complex and recovery of trimethylamine - Google Patents
Production of trimethylamine-sulfur trioxide complex and recovery of trimethylamineInfo
- Publication number
- JPH0324039A JPH0324039A JP15864689A JP15864689A JPH0324039A JP H0324039 A JPH0324039 A JP H0324039A JP 15864689 A JP15864689 A JP 15864689A JP 15864689 A JP15864689 A JP 15864689A JP H0324039 A JPH0324039 A JP H0324039A
- Authority
- JP
- Japan
- Prior art keywords
- trimethylamine
- chlorosulfonic acid
- complex
- reaction
- water
- 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000011084 recovery Methods 0.000 title description 4
- DXASQZJWWGZNSF-UHFFFAOYSA-N n,n-dimethylmethanamine;sulfur trioxide Chemical compound CN(C)C.O=S(=O)=O DXASQZJWWGZNSF-UHFFFAOYSA-N 0.000 title description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005703 Trimethylamine hydrochloride Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000001180 sulfating effect Effects 0.000 abstract description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002472 Starch Polymers 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 3
- 239000001913 cellulose Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000008107 starch Substances 0.000 abstract description 3
- 235000019698 starch Nutrition 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 2
- 150000004676 glycans Chemical class 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 229920001282 polysaccharide Polymers 0.000 abstract description 2
- 239000005017 polysaccharide Substances 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract 3
- 150000001412 amines Chemical class 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- -1 hexane and N-octane Chemical compound 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、トリメチルアミン・三酸化イオウ錯体の改良
された製造法に関するものである。更に詳しくは、本発
明は例えばアルコール類、澱粉やセルロース等の多糖類
を硫酸化するのに重要なトリメチルアミン・二酸化イオ
ウ錯体を製造する方法に関するものである．
〔従来の技術〕
従来トリメチルアミン・三酸化イオウ錯体を製造する方
法として大別すると二つに分けることが出来る．その一
つは二酸化イオウとトリメチルアミンとを反応させる方
法であり、もう一つはクロルスルホン酸とトリメチルア
ミンとを反応させる方法である。前者の方法としては二
酸化イオウとトリメチルアミンとを気相中で直接反応さ
せる方法（Ｂｅｌｇ． ６６４，４１３ （１９６５）
）や液体二酸化イオウを疎水性有機溶媒で希釈してト
リメチルアミンと反応させる方法（Ｚｈ， Ｎｅａｒｇ
ａｎ．κｈｉｍ ７， １３１６−１９（１９６２）
）が知られている．
一方クロルスルホン酸を使用する方法は特開昭５９−１
３４７３１号に開示されており、この方法に於いてはク
ロルスルホン酸とトリメチルアミンとは等モルで且つ冷
却下で反応を行わせている．しかしながら上記の方法に
よって得られる生或物はいずれも収率が低く、且つ錯体
自身の純度も低いためそのままで硫酸化剤として用いる
ことは困難である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved method for producing a trimethylamine-sulfur trioxide complex. More specifically, the present invention relates to a method for producing trimethylamine/sulfur dioxide complex, which is important for sulfating polysaccharides such as alcohols, starch, and cellulose. [Prior art] Conventional methods for producing trimethylamine/sulfur trioxide complexes can be roughly divided into two types. One method is to react sulfur dioxide and trimethylamine, and the other method is to react chlorosulfonic acid and trimethylamine. The former method involves directly reacting sulfur dioxide and trimethylamine in the gas phase (Belg. 664, 413 (1965)).
) and a method in which liquid sulfur dioxide is diluted with a hydrophobic organic solvent and reacted with trimethylamine (Zh, Nearg
an. κhim 7, 1316-19 (1962)
)It has been known. On the other hand, the method using chlorosulfonic acid was disclosed in Japanese Patent Application Laid-Open No. 59-1
No. 34731, in which chlorosulfonic acid and trimethylamine are used in equimolar amounts and the reaction is carried out under cooling. However, the raw material obtained by the above method has a low yield and the purity of the complex itself is low, so it is difficult to use it as it is as a sulfating agent.
本発明の目的は、クロルスルホン酸とトリメチルアミン
を反応させ、高純度のトリメチルアミン・三酸化イオウ
錯体を高収率で製造する方法を提供することにある。An object of the present invention is to provide a method for producing a highly purified trimethylamine/sulfur trioxide complex in high yield by reacting chlorosulfonic acid and trimethylamine.
本発明者らは、高純度のトリメチルアミン・三酸化イオ
ウ錯体を製造する方法について鋭意研究を重ねた結果、
（イ）トリメチルアミン・三酸化イオウ錯体の収率及び
純度は、クロルスルホン酸とトリメチルアξンとの仕込
モル比と反応温度及び反応後の熟威温度に著しく影響を
受けること、
（口）適切な条件で反応して得られた生或物を水又はア
ルカリ水溶液で処理することにより、結晶が容易に析出
すること、
（ハ）生底物と濾別した濾液の水層に高濃度の・水酸化
アルカリ水溶液を加えることにより、該濾液中にトリメ
チルアミン・塩酸塩として溶解しているトリメチルアミ
ンを容易に回収しうろこと、
を見出し、これらの知見に基づいて本発明をなすに至っ
た．
即ち本発明は疎水性有機溶媒中クロルスルホン酸１モル
に対し、トリメチルアミン１．８〜２．３モルを用い少
なくとも５℃以下の温度で反応させ、次いでこの反応液
を水又はアルカリ水溶液で処理することを特徴とするト
リメチルアミン・三酸化イオウ錯体の製造法、及び該濾
液中からトリメチルアミンを回収することを特徴とする
トリメチルアミンの回収法に係るものである．
〔発明の作用〕
本発明によれば、クロルスルホン酸に対し１．８〜２．
３倍モルのトリメチルアミンを使用し、特に５℃以下の
温度で反応せしめ、且つ反応で副生ずるトリメチルア逅
ン・塩酸塩を水又はアルカリ水溶液中に溶解させ、生戒
したトリメチルアミン・三酸化イオウ錯体を結晶として
取り出すことができるので高収率で高純度のトリメチル
アミン・三酸化イオウを得られると共に、容易に生或物
の分離・精製を行うことができる。しかも、水又はアル
カリ水溶液に溶解したトリメチルアミン・塩酸塩からト
リメチルアミンを容易に収率よく回収することができ、
この回収したトリメチルアミンを再度上記反応の出発原
料として利用でき、従来の方法と比較して工業的にも極
めて有利な方法である。As a result of extensive research into the method of producing a highly pure trimethylamine/sulfur trioxide complex, the present inventors have found that (a) the yield and purity of the trimethylamine/sulfur trioxide complex are as follows: (2) By treating the raw material obtained by reacting under appropriate conditions with water or an aqueous alkaline solution, (c) By adding a highly concentrated aqueous alkali hydroxide solution to the aqueous layer of the filtrate separated from the raw bottom matter, trimethylamine dissolved in the filtrate as trimethylamine/hydrochloride can be removed. We have discovered that scales can be easily recovered, and based on these findings, we have accomplished the present invention. That is, in the present invention, 1 mole of chlorosulfonic acid in a hydrophobic organic solvent is reacted with 1.8 to 2.3 moles of trimethylamine at a temperature of at least 5° C., and then this reaction solution is treated with water or an aqueous alkali solution. The present invention relates to a method for producing a trimethylamine/sulfur trioxide complex, which is characterized by the above, and a method for recovering trimethylamine, which is characterized by recovering trimethylamine from the filtrate. [Action of the Invention] According to the present invention, chlorosulfonic acid has a concentration of 1.8 to 2.
A trimethylamine/sulfur trioxide complex prepared by using 3 times the mole of trimethylamine and reacting at a temperature of 5°C or lower, and dissolving trimethylamine/hydrochloride, which is a by-product of the reaction, in water or an alkaline aqueous solution. Since trimethylamine and sulfur trioxide can be extracted as crystals, high yield and high purity trimethylamine/sulfur trioxide can be obtained, and the raw material can be easily separated and purified. Moreover, trimethylamine can be easily recovered in good yield from trimethylamine hydrochloride dissolved in water or aqueous alkaline solution.
This recovered trimethylamine can be used again as a starting material for the above reaction, making this method industrially extremely advantageous compared to conventional methods.
本発明において使用するクロルスルホン酸は、不純物を
取り除くため脱水蒸留して用いるのが望ましい。又、疎
水性有機溶媒としては、クＩｊロホルム、四塩化炭素、
二塩化メチレン、二塩化エチレン等のハロゲン化脂肪族
炭化水素、ヘキサン、Ｎ−オクタン等の脂肪族炭化水素
、メヂルエチルケトンの如き脂肪族ケトン類を用いるこ
とができるが、溶媒回収の容易さのために二塩化エチレ
ンが好ましい．
クロルスルホン酸とトリメチルアごンの配合比は重要で
あって、クロルスルホン酸ｌモルに対しトリメチルアミ
ンを１．８〜２．３モル、好ましくは１．９〜２．１モ
ルの範囲で用いることが必要である．このトリメチルア
ミンの配合比がクロルスルホン酸１モルに対し、１．８
モル未満ではトリメチルアミン・三酸化イオウ錯体の生
或収率が低下し、２．３モルを超えるとトリメチルアミ
ン・二酸化イオウ錯体の純度が著しく低下する．
クロルスルホン酸とトリメチルアミンの反応液を処理す
るのに用いるアルカリ溶液としては水酸化ナトリウム、
水酸化カリウム、水酸化カルシウム、水酸化マグネシウ
ムの如きアルカリ又はアルカリ土邦金属の水酸化物が挙
げられるが、実用的には水酸化ナトリウムが好ましい．
この反応液を水で処理する場合、水の使用量はクロルス
ルホン酸に対し２〜３倍量（重量）、又アルカリ水溶液
で処理する場合のアルカリの使用量はクロルスルホン酸
に対し、１．０〜１．５倍当量が最も適当である．
一方、反応温度については少なくとも５℃以下好ましく
はＯ′Ｃで行う必要があり、５℃を超えるとトリメチル
アミン・三酸化イオウの生或収率は著しく低下する．又
該反応液をアルカリ水溶液に加えて中和する場合、生戒
したトリメチルアもン・三酸化イオウ錯体の加水分解を
防ぐため５℃以下で行うことが望ましい．
又反応時間についてはクロルスルホン酸とトリメチルア
主ンの配合比及び反応時間によって左右されるが、通常
１〜５時間、好ましくは２〜３時間である．
又熟威温度は０〜５℃が好ましい．この熟威については
反応終了後１〜２時間位行う．生成物を濾別した濾液の
水層に高濃度の水酸化ナトリウム水溶液を加えてトリメ
チルアミンを回収する場合には、！＆離するトリメチル
アミンを効率よく吸収させるため、減圧下０℃以下で行
うことが好ましい．又この場合、使用する水酸化ナトリ
ウム水溶液の濃度は３５〜４８％が好ましく、使用量は
トリメチルアミン・塩酸塩に対し１．０〜２．０倍当量
が適当である．
〔発明の効果〕
本発明方法はクロルスルホン酸とほぼ２倍モルのトリメ
チルアミンを用いて低温で反応し、次いで水又はアルカ
リ水溶液で処理することにより、高純度のトリメチルア
ミン・三酸化イオウ錯体を収率よく製造することができ
、又該反応濾液からトリメチルアミンを回収して再使用
することができ、工業的に極めて優れた方法である。The chlorosulfonic acid used in the present invention is preferably used after dehydration and distillation in order to remove impurities. In addition, examples of hydrophobic organic solvents include chloroform, carbon tetrachloride,
Halogenated aliphatic hydrocarbons such as methylene dichloride and ethylene dichloride, aliphatic hydrocarbons such as hexane and N-octane, and aliphatic ketones such as methyl ethyl ketone can be used, but the ease of solvent recovery Therefore, ethylene dichloride is preferred. The blending ratio of chlorsulfonic acid and trimethylamine is important, and trimethylamine should be used in a range of 1.8 to 2.3 moles, preferably 1.9 to 2.1 moles per mole of chlorsulfonic acid. is necessary. The blending ratio of trimethylamine is 1.8 to 1 mole of chlorosulfonic acid.
If it is less than 2.3 moles, the production yield of the trimethylamine/sulfur trioxide complex will decrease, and if it exceeds 2.3 moles, the purity of the trimethylamine/sulfur dioxide complex will decrease significantly. The alkaline solution used to treat the reaction solution of chlorosulfonic acid and trimethylamine includes sodium hydroxide,
Examples include hydroxides of alkali or alkaline earth metals such as potassium hydroxide, calcium hydroxide, and magnesium hydroxide, but sodium hydroxide is practically preferred.
When this reaction solution is treated with water, the amount of water used is 2 to 3 times the amount (by weight) of chlorosulfonic acid, and when the reaction solution is treated with an aqueous alkali solution, the amount of alkali used is 1. 0 to 1.5 times equivalent is most appropriate. On the other hand, the reaction temperature must be at least 5°C or lower, preferably O'C; if it exceeds 5°C, the production or yield of trimethylamine/sulfur trioxide will drop significantly. When neutralizing the reaction solution by adding it to an alkaline aqueous solution, it is preferable to carry out the reaction at 5°C or lower to prevent hydrolysis of the trimethylamone/sulfur trioxide complex. The reaction time depends on the blending ratio of chlorosulfonic acid and trimethylamine and the reaction time, but is usually 1 to 5 hours, preferably 2 to 3 hours. The ripening temperature is preferably 0 to 5°C. This ripening is carried out for about 1 to 2 hours after the reaction is completed. When trimethylamine is recovered by adding a highly concentrated aqueous sodium hydroxide solution to the aqueous layer of the filtrate after filtering the product,! & In order to efficiently absorb the trimethylamine to be released, it is preferable to carry out the reaction under reduced pressure at a temperature below 0°C. In this case, the concentration of the aqueous sodium hydroxide solution used is preferably 35 to 48%, and the appropriate amount is 1.0 to 2.0 times equivalent to trimethylamine hydrochloride. [Effects of the Invention] The method of the present invention uses chlorosulfonic acid and approximately twice the molar amount of trimethylamine to react at low temperature, and then treats with water or an aqueous alkali solution, thereby producing a high purity trimethylamine/sulfur trioxide complex in high yield. This method is industrially excellent because it can be easily produced, and trimethylamine can be recovered and reused from the reaction filtrate.
本発明により得られた高純度のトリメチルアミン・二酸
化イオウ錯体はアルコール類、或いは澱粉やセルロース
等の多ＩＩ類の硫酸化剤として好適に用いられる．
〔実施例〕
次に実施例によって本発明を更に詳細に説明するが、本
発明はその要旨を逸脱しない限り以下の実施例に何等限
定されるものではない．実権例１
トリメチルアミン３７．７ｇ（０．６４モル）を１．２
−ジクロ口エタン２００ｍ ｌ に０℃以下で溶解し、
これに冷却下クロルスルホン酸３７．２ｇ（０．３２モ
ル）を滴下した。滴下の速度は反応混合物の温度がＯ″
Ｃ付近に保たれるように調節した．滴下後この反応液を
２Ｎ一水酸化ナトリウム水溶液１９０ｎ＋１ （０．３
８モル）に冷却下撹拌しながら加えた。投入後０〜５℃
に冷却しながら１時間撹拌し、析出した結晶を濾過、乾
燥して梢製トリメチルアミン・三酸化イオウ錯体３９．
３ｇ（収率８Ｂ．３％）が得られた．この精製物の融点
は２４０℃であった．
次に濾別した濾液を分層し、その水府２００ｇに４８％
水酸化ナ｝ ＩＪウム水溶液４０．０ｇ（０．４８モル
）を滴下し、遊離したトリメチルアミンを１．２−ジク
ロロエタンにＯ′Ｃ以下で吸収させて回収した。回収率
は７８．５％（対トリメチルアミン・塩酸塩）であった
．
以下上記と同様の操作でクロルスルホン酸とトリメチル
アミンの種々の仕込モル比について実験を行った。これ
等の結果を第１表に示す。The highly purified trimethylamine/sulfur dioxide complex obtained by the present invention is suitably used as a sulfating agent for alcohols, or poly-class II materials such as starch and cellulose. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it deviates from the gist thereof. Practical example 1 37.7g (0.64 mol) of trimethylamine was added to 1.2
- dissolved in 200 ml of dichloroethane at below 0°C,
To this was added dropwise 37.2 g (0.32 mol) of chlorosulfonic acid while cooling. The rate of dropping is determined when the temperature of the reaction mixture is O''
Adjustments were made to keep it near C. After dropping, this reaction solution was diluted with 2N sodium monohydroxide aqueous solution 190n+1 (0.3
8 mol) while stirring under cooling. 0~5℃ after charging
The precipitated crystals were filtered and dried to obtain the trimethylamine/sulfur trioxide complex 39.
3g (yield 8B.3%) was obtained. The melting point of this purified product was 240°C. Next, separate the filtered filtrate into layers, and add 48% to 200g of the filtrate.
40.0 g (0.48 mol) of an aqueous sodium hydroxide solution was added dropwise, and the liberated trimethylamine was absorbed into 1,2-dichloroethane at a temperature below O'C and recovered. The recovery rate was 78.5% (based on trimethylamine/hydrochloride). Hereinafter, experiments were conducted with various molar ratios of chlorosulfonic acid and trimethylamine in the same manner as above. These results are shown in Table 1.
第１表
実施例２
トリメチルアくン３７．Ｏｇ（０．６３モル）を１．２
−ジクロロエタン２００ｍｉにＯ℃以下で溶解し、これ
に実施例１と同様にクロロスルホン酸３６．５ｇ（０．
３２モル）を滴下した。滴下後Ｏ〜５℃で１時間撹拌し
、水７４．０ｇを投入し、１５分撹拌した。撹拌後析出
した結晶を濾過し、その結晶を水３７．０ｇで洗浄し乾
燥して４１．１ｇ（収率９４．２％）の桔製トリメチル
アミン・二酸化イオウ錯体を得た．この精製物の融点は
２３８〜２３９（“Ｃ）であった。Table 1 Example 2 Trimethylakun 37. 1.2 Og (0.63 mol)
-Dissolved in 200 mi of dichloroethane at 0°C or lower, and added 36.5 g (0.
32 mol) was added dropwise. After dropping, the mixture was stirred at 0 to 5°C for 1 hour, 74.0 g of water was added, and the mixture was stirred for 15 minutes. After stirring, the precipitated crystals were filtered, and the crystals were washed with 37.0 g of water and dried to obtain 41.1 g (yield: 94.2%) of a trimethylamine/sulfur dioxide complex produced in a box. The melting point of this purified product was 238-239 ("C).
次に実施例１と同様の操作でトリメチルアくンを回収し
た．回収率は８５．６％（対トリメチルアくン・塩酸塩
）であった．
比較例ｌ
トリメチルアミン２０．０ｇ （０．３４モル）を１．
２−ジクロロエタン２００ｍｌに溶解し、これに冷却下
１．２−ジクロロエタン１２５ｍｌに三酸化イオウ１８
．１ｇ（０．２３モル）を溶かしたものを滴下した．滴
下後、１時間撹拌し水４０．０ｇを投入した．投入後析
出した結晶を濾過し、４０．０ｇの水で洗浄し乾燥して
２０． ４ｇ （収率６５．２％）のトリメチルアミン
・三酸化イオウ錯体が得られた．このものの融点は２２
３〜２２８℃であった．
比較例２
トリメチルアミン２３．６ｇ（０．４０モル）を１．２
−ジクロロエタン６０＋ｗｌに溶解し、これに冷却下ク
ロルスルホン酸４６．６ｇ（０．４０モル）を滴下した
。この反応液を２ Ｎ −ＮａＯＨ２４０ｍｌ （０．
４８モル）に冷却下撹拌しながら加えた。投入後ｌ時間
撹拌した後Ｏ′Ｃに冷却し、析出した結晶を濾過し乾燥
して４２．２ｇ（収率７５．９％）のトリメチルアミン
・三酸化イオウ錯体が得られた。このものの融点は２２
０〜２２５℃であった．
（以 上）Next, trimethylamine was recovered in the same manner as in Example 1. The recovery rate was 85.6% (based on trimethylamine hydrochloride). Comparative Example 1 20.0 g (0.34 mol) of trimethylamine was added to 1.
Dissolved in 200 ml of 2-dichloroethane, and added 18 sulfur trioxide to 125 ml of 1,2-dichloroethane under cooling.
．． A solution of 1 g (0.23 mol) was added dropwise. After dropping, the mixture was stirred for 1 hour and 40.0 g of water was added. After the addition, the precipitated crystals were filtered, washed with 40.0 g of water, and dried. 4 g (yield: 65.2%) of trimethylamine/sulfur trioxide complex was obtained. The melting point of this thing is 22
The temperature ranged from 3 to 228°C. Comparative Example 2 23.6 g (0.40 mol) of trimethylamine was added to 1.2
- It was dissolved in 60+wl of dichloroethane, and 46.6 g (0.40 mol) of chlorosulfonic acid was added dropwise thereto under cooling. This reaction solution was mixed with 240ml of 2N-NaOH (0.
48 mol) while stirring under cooling. After the addition, the mixture was stirred for 1 hour, cooled to O'C, and the precipitated crystals were filtered and dried to obtain 42.2 g (yield 75.9%) of trimethylamine/sulfur trioxide complex. The melting point of this thing is 22
The temperature ranged from 0 to 225°C. (that's all)
Claims (3)
し、トリメチルアミン１．８〜２．３モルを用い、少な
くとも５℃以下の温度で反応せしめ、次いでこの反応液
を水又はアルカリ水溶液で処理することを特徴とするト
リメチルアミン・三酸化イオウ錯体の製造方法。(1) Using 1.8 to 2.3 moles of trimethylamine per mole of chlorosulfonic acid in a hydrophobic organic solvent, react at a temperature of at least 5°C or lower, and then treat the reaction solution with water or an aqueous alkali solution. A method for producing a trimethylamine/sulfur trioxide complex.
し、トリメチルアミン１．８〜２．３モルを用い、少な
くとも５℃以下の温度で反応せしめ、次いでこの反応液
を水又はアルカリ水溶液で処理し、析出する結晶を分離
した後、更にこの濾液にアルカリを添加して、トリメチ
ルアミンを回収することを特徴とするトリメチルアミン
の回収方法。(2) Using 1.8 to 2.3 moles of trimethylamine per mole of chlorosulfonic acid in a hydrophobic organic solvent, react at a temperature of at least 5°C or less, and then treat the reaction solution with water or an aqueous alkali solution. and after separating the precipitated crystals, alkali is further added to the filtrate to recover trimethylamine.
項（１）に記載の方法の出発原料として使用することを
特徴とする請求項（１）に記載の製造方法。(3) The production method according to claim (1), characterized in that the trimethylamine recovered in claim (2) is used as a starting material for the method according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15864689A JPH0324039A (en) | 1989-06-21 | 1989-06-21 | Production of trimethylamine-sulfur trioxide complex and recovery of trimethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15864689A JPH0324039A (en) | 1989-06-21 | 1989-06-21 | Production of trimethylamine-sulfur trioxide complex and recovery of trimethylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0324039A true JPH0324039A (en) | 1991-02-01 |
Family
ID=15676258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15864689A Pending JPH0324039A (en) | 1989-06-21 | 1989-06-21 | Production of trimethylamine-sulfur trioxide complex and recovery of trimethylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0324039A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884914A (en) * | 2014-12-26 | 2016-08-24 | 厦门大学 | Starch sulphate and novel process for synthesizing starch sulphate salt |
-
1989
- 1989-06-21 JP JP15864689A patent/JPH0324039A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884914A (en) * | 2014-12-26 | 2016-08-24 | 厦门大学 | Starch sulphate and novel process for synthesizing starch sulphate salt |
| CN105884914B (en) * | 2014-12-26 | 2021-02-19 | 厦门大学 | Starch sulfate and synthesis process of salt thereof |
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