JP3735914B2 - Method for producing aminoester compound - Google Patents
Method for producing aminoester compound Download PDFInfo
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- JP3735914B2 JP3735914B2 JP33863395A JP33863395A JP3735914B2 JP 3735914 B2 JP3735914 B2 JP 3735914B2 JP 33863395 A JP33863395 A JP 33863395A JP 33863395 A JP33863395 A JP 33863395A JP 3735914 B2 JP3735914 B2 JP 3735914B2
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- 150000001875 compounds Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 aminoalcohol compound Chemical class 0.000 claims description 53
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000005457 ice water Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 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 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- VCRFJFCIUBEUHO-UHFFFAOYSA-N C(C)(=O)NCCC(CS(=O)(=O)CC(CCNC(C)=O)O)O Chemical compound C(C)(=O)NCCC(CS(=O)(=O)CC(CCNC(C)=O)O)O VCRFJFCIUBEUHO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、各種の工業製品、特に撥水撥油加工剤、ハロゲン化銀写真硬化剤、界面活性剤、染料、医薬及び農薬等の中間体として有用なアミノエステル化合物の製造法に関する。
【０００２】
【従来の技術】
脂肪族のアミノアルコール化合物を硫酸エステル化するとき、従来は、１）大過剰の濃硫酸中でアミノアルコール化合物をエステル化する方法、２）アミノアルコール化合物のＮ−アセチル化物を塩酸又は希硫酸中で加水分解後、大過剰の濃硫酸中でエステル化する方法、３）クロルスルホン酸とアミノアルコール化合物をＮ−メチルピロリドン中で、１０〜８０℃で反応させる方法等で行われていた。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記１）の方法では、原料である脂肪族のアミノアルコール化合物の乾燥が必要なために操作が煩雑であるという欠点があり、上記２）の方法では、原料である脂肪族アミノアルコール化合物のＮ−アセチル化物の乾燥が必要なうえに目的化合物であるアミノエステル化合物の取出収率が低く、何れも工業的には有利とはいえなかった。また、上記３）の方法では、反応液中の過剰のクロルスルホン酸を先ず氷水で分解し、分解により得られた液を中和し、次いで、中和された液からアミノエステル化合物をＮ−メチルピロリドン以外の適当な溶媒により抽出する必要があるばかりでなく、例えば、蒸留といった方法を用いてＮ−メチルピロリドンをも回収する必要があり、工業的に有利な方法であるとは言えなかった。
【０００４】
【課題を解決するための手段】
本発明者らは、アミノエステル化合物の工業的にも有利な改良製法を鋭意検討した結果、アミノアルコール化合物又はそのＮ−アセチル化物と、これらの化合物に対して特定量の硫酸又は発煙硫酸とを、加熱且つ減圧条件で有機溶媒等の反応溶媒を使用せずに、副生成物である水又は水と酢酸を留去しながら反応させると、煩雑な操作を必要とせずに反応が行えること、及び、反応生成物の取出収率が著しく向上することを見出して、本発明を完成するに至った。
即ち、本発明は、遊離アミンの形で表すと、アミノアルコール化合物（ＩＩ）又はそのＮ−アセチル化物を、これらの化合物におけるヒドロキシ基１個当りの理論量に対して１．２５〜１０倍モル量の硫酸又は発煙硫酸と、１００〜１８０℃の範囲に加熱し、且つ、５〜５０ｍｍＨｇの減圧条件で、水又は水と酢酸とを留去しながら反応させ、反応で得られた反応生成物を８０〜１５０℃に保温し、該保温された生成物を水又は氷で処理することを特徴とする、遊離アミンの形で表すとアミノエステル化合物（Ｉ）の製造方法を提供するものである。
Ｈ−Ｎ（Ｒ2）−Ｗ2−ＳＯ2ＣＨ2ＣＨ2ＯＹ （Ｉ）
Ｈ−Ｎ（Ｒ 1 ）−Ｗ 1 −ＳＯ 2 ＣＨ 2 ＣＨ 2 ＯＨ （ＩＩ）
［式中、Ｗ1は置換されていてもよく、−Ｏ−又は−ＮＲ3−（ここで、Ｒ3は水素原子又はＣ1〜Ｃ4アルキル基を表す。）を含んでいてもよい直鎖状又は分枝状のＣ2〜Ｃ6アルキレン基を表し、Ｒ１は水素原子、置換されていてもよいＣ1〜Ｃ4アルキル基、置換されていてもよいフェニル基又は−Ｗ１−ＳＯ2ＣＨ2ＣＨ2ＯＹの基を表す。
Ｗ２は置換されていてもよく、−Ｏ−又は−ＮＲ3−（Ｒ3は前記と同じ意味を表す）を含んでいてもよい直鎖状又は分枝状のＣ2〜Ｃ6アルキレン基を表し、Ｒ2は水素原子、置換されていてもよいＣ1〜Ｃ4アルキル基、置換されていてもよいフェニル基又は−Ｗ2−ＳＯ2ＣＨ2ＣＨ2ＯＹの基を表し、Ｙは−ＳＯ3Ｈ又はそのアルカリ金属若しくはアルカリ土類金属塩を表す。］
【０００５】
【発明の実施の形態】
以下、本発明について詳細に説明する。
アミノアルコール化合物（ＩＩ）又はそのＮ−アセチル化物は遊離アミンでもよく、硫酸塩等の鉱酸塩を用いてもよい。これらの遊離アミン及び鉱酸塩は、含水状態のものでも乾燥状態のものでも使用可能である。また、アミノアルコール化合物及びそのＮ−アセチル化物はＮａＣｌ、Ｎａ2ＳＯ4等の無機塩を含んでいてもよい。本発明において前記のアミノアルコール化合物のアセチル化物を出発原料として用いる場合は、アセチルアミノ基の加水分解により副生する酢酸を反応系外へ除く必要がある。
【０００６】
反応に用いる硫酸濃度は特に制限されないが、好ましくは２０〜１００％、より好ましくは４０〜９８％の濃度に調整される。発煙硫酸を用いる場合、その濃度は特に限定されない。また、硫酸と発煙硫酸とを併用してもよい。硫酸又は発煙硫酸の使用量は１００％硫酸換算で、アミノアルコール化合物（ＩＩ）又はそのＮ−アセチル化物のヒドロキシ基１個当りの理論量に対して１．２５〜１０倍モル量であり、好ましくは１．２５〜５倍モル量である。従って、アミノアルコール化合物（ＩＩ）又はそのＮ−アセチル化物が２個以上のヒドロキシ基を有する場合は、硫酸又は発煙硫酸の使用量は上記の（１．２５〜１０倍モル量）×（ヒドロキシ基の個数）である。
硫酸又は発煙硫酸の使用量がヒドロキシ基１個当たりの理論量に対して１．２５倍モル量未満では反応生成物の流動性が乏しくてアミノ酸誘導体の取り出しが困難になり、取り出し収率が低下する傾向がある。一方、硫酸又は発煙硫酸の使用量がヒドロキシ基１個当たりの理論量に対して１０倍モル量を越えると、反応速度が遅くなる傾向がある。
【０００７】
本発明においては、アミノアルコール化合物（ＩＩ）又はそのＮ−アセチル化物、及び硫酸又は発煙硫酸の仕込順序は特に限定されるものではない。
反応温度は、反応速度の観点からは高温である方が一般的に好ましいが、必要以上の高温では副反応が生じてアミノエステル化合物（Ｉ）の収率が低下する傾向があるので、１００〜１８０℃である。減圧度は、設定された反応温度において水又は水及び酢酸の反応系外への留去が可能になるように設定され、５〜５０ｍｍＨｇである。反応系中に存在する水又は水及び酢酸の反応系外への留去は、加熱及び減圧条件で、通常は攪拌により行われる。本発明の方法は通常の缶、槽及び釜等の反応器を用いる回分式方法により行うことができる。
【０００８】
一般式（ＩＩ）においてＷ1で表される直鎖状又は分枝状のＣ2〜Ｃ6アルキレン基の置換基としては、例えば、ハロゲン原子、ヒドロキシ基、スルファート基、カルボキシ基、シアノ基及びスルホ基等が挙げられる。
一般式（Ｉ）においてＷ2で表される直鎖状又は分枝状のＣ2〜Ｃ6アルキレン基の置換基としては、例えばハロゲン原子、アルカリ金属若しくはアルカリ土類金属塩の形で存在してもよいスルファート基、アルカリ金属若しくはアルカリ土類金属塩の形で存在してもよいカルボキシ基、シアノ基、及びアルカリ金属若しくはアルカリ土類金属塩の形で存在してもよいスルホ基等が挙げられる。
遊離アミンの形で表すと、アミノアルコール化合物（ＩＩ）は、公知の方法、例えば対応するクロロまたはブロモアルキルアミン類とメルカプトエタノールとを縮合させ、次いで、得られたチオエーテル化合物を過酸化水素で酸化する方法により製造される。アミノアルコール化合物（ＩＩ）のＮ−アセチル化物の場合は、縮合で得られたチオエーテル化合物を無水酢酸でアセチル化後、得られたアセチル化生成物を過酸化水素で酸化する方法により製造される。アミノアルコール化合物（ＩＩ）及びそのＮ−アセチル化物としては、例えば、遊離アミンの形で表すと、下記のような化合物が例示される。
【０００９】
Ｈ2ＮＣ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ3Ｈ6ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ4Ｈ8ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ5Ｈ10ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ6Ｈ12ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ2Ｈ4ＯＣ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ2Ｈ4ＯＣ3Ｈ6ＳＯ2Ｃ2Ｈ4ＯＨ
ＨＮ（Ｃ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ）2
ＨＮ（ＣＨ3）Ｃ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
ＨＮ（Ｃ2Ｈ5）Ｃ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
ＨＮ（Ｃ2Ｈ5）Ｃ3Ｈ6ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣＨ（Ｃ2Ｈ5）ＣＨ2ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ2Ｈ4ＮＨＣ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
Ｈ2ＮＣ2Ｈ4ＮＨＣＨ（ＣＨ3）ＣＨ2ＳＯ2Ｃ2Ｈ4ＯＨ
ＣＨ3ＣＯＮＨＣ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
ＣＨ3ＣＯＮＨＣ3Ｈ6ＳＯ2Ｃ2Ｈ4ＯＨ
ＣＨ3ＣＯＮＨＣ4Ｈ8ＳＯ2Ｃ2Ｈ4ＯＨ
ＨＮ（Ｃ6Ｈ5）−Ｃ2Ｈ4ＳＯ2Ｃ2Ｈ4ＯＨ
【００１０】
アミノエステル化合物（Ｉ）の取出は、好ましくは、反応終了後に得られた反応生成物を水又は氷で処理することにより行われる。
具体的には、例えば氷水及び冷水等の中に、或いは、例えば重曹、炭酸水素カリウム、ソーダ灰、炭酸カリウム、水酸化ナトリウム及び水酸化カリウム等のアルカリを加えた氷水又は冷水の中に、好ましくは８０〜１５０℃に保温した反応生成物を加えて、液体の状態で取り出すことができる。氷水又は冷水の中に、前記反応生成物を加えて液体の状態で得た場合、得られた液体に、前記アルカリを添加してもよい。これらの液体から、濃縮、凍結乾燥及び濾過等の公知の方法により、アミノエステル化合物（Ｉ）を単離することもできる。
特に、撥水撥油加工剤、ハロゲン化銀写真硬化剤、界面活性剤等の用途には、アミノエステル化合物（Ｉ）はアルカリ中和後のものを用いることが好ましい。
【００１１】
【実施例】
次に、本発明を実施例により更に具体的に説明する。例中の部及び％は、それぞれ重量部及び重量％であることを示す。
【００１２】
実施例１
９８％硫酸１０．０部と２５％Ｎ−エチル−［２−（２−ヒドロキシエチルスルホニル）エチル］アミン硫酸塩水溶液７０．８部を撹拌しながら３０ｍｍＨｇまで減圧し、１００℃まで昇温した後、副生する水を留去することにより水を反応系外へ除きながら、１００℃で反応を続けた。反応終了後、９０〜１１０℃に保温した反応生成物を氷水１００部中に注いで、得られた水溶液をソーダ灰でｐＨ１〜２に中和した。Ｎ−エチル−［２−（２−スルファートエチルスルホニル）エチル］アミンの生成率は９８％であり、他に少量のＮ−エチル−［２−（２−ヒドロキシエチルスルホニル）エチル］アミン硫酸塩を含んでいた。
【００１３】
実施例２
９８％硫酸１０．０部に代えて３０％発煙硫酸９．２部を用いても、実施例１と同様の生成率でＮ−エチル−［２−（２−スルファートエチルスルホニル）エチル］アミンが得られた。
【００１４】
実施例３
９８％硫酸１６．８部とアミノプロピル−２−ヒドロキシエチルスルホン硫酸塩２５．９部を撹拌しながら４０ｍｍＨｇの減圧下にて、１５０〜１５５℃まで加熱し副生する水を留去することによって水を反応系外へ除きながら同温度で反応を続けて反応を終了させた。反応終了後、１２０〜１３０℃に保温した反応生成物を氷水１００部中に注いで、得られた水溶液をソーダ灰でｐＨ１〜２に中和した。アミノプロピル−２−スルファートエチルスルホンの生成率は９８％であり、他に少量のアミノプロピル−２−ヒドロキシエチルスルホン硫酸塩を含んでいた。
【００１５】
実施例４
ビス−［２−（２−ヒドロキシエチルスルホニル）エチル］アミン硫酸塩の２０％水溶液３３６．８部、珪藻土５．０部及び９８％硫酸２０．８部の混合物を撹拌下に５０ｍｍＨｇまで減圧して、副生する水を留去することにより水を反応系外へ除きながら、徐々に１１０〜１２０℃まで昇温後、同温度で反応を続けた。反応終了後、得られた反応生成物を氷水１００部中に注ぎ、次いでソーダ灰でｐＨ１〜２に中和した。ビス−［２−（２−スルファートエチルスルホニル）エチル］アミンの生成率は９７％であった。
【００１６】
実施例５
アセチルアミノエチル−２−ヒドロキシエチルスルホンの３０％水溶液６５０部及び９８％硫酸１５０部の混合物を撹拌しながら、５０ｍｍＨｇの減圧下で１２０〜１２５℃まで加熱し、副生する酢酸及び水を留去することによって酢酸及び水を反応系外へ除きながら同温度で反応を続けて反応を終了させた。得られた反応生成物を氷水５００部中に注ぎ、次いでソーダ灰でｐＨ３〜６に中和した。アミノエチル−２−スルファートエチルスルホンの生成率は９５％であった。
【００１７】
実施例６〜１０
アミノプロピル−２−ヒドロキシエチルスルホン硫酸塩に代えて、下表第２欄に記載の化合物の等モル量を用いる以外は実施例３と同様にして、遊離アミンの形で表すと、下表第３欄に記載の化合物を収率良く得た。
【００１８】
【発明の効果】
本発明の方法によれば、撥水撥油加工剤、ハロゲン化銀写真硬化剤及び界面活性剤等の各種の工業製品の中間体として有用な一般式（Ｉ）で示されるアミノエステル化合物を工業的にも有利に製造することができる。
【００２０】
参考例１
実施例１で得られた中和後の水溶液を凍結乾燥して固体のＮ−エチル−［２−（２−スルファートエチルスルホニル）エチル］アミンを収率９７.５％で得た。
これを、トリエチルアミンの存在下にポリフルオロ−１−オクタンスルホニルフルオライドと反応させ、反応終了後、アルカリを添加して下式
Ｃ８Ｆ１７ＳＯ２Ｎ（Ｃ２Ｈ５）Ｃ２Ｈ４ＳＯ２ＣＨ＝ＣＨ２
で示される撥水撥油加工剤（融点１２３〜１２５℃）を得た。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing amino ester compounds useful as intermediates for various industrial products, particularly water / oil repellent finishing agents, silver halide photographic hardeners, surfactants, dyes, pharmaceuticals and agricultural chemicals.
[0002]
[Prior art]
When an aliphatic aminoalcohol compound is sulfated, conventionally, 1) a method of esterifying an aminoalcohol compound in a large excess of concentrated sulfuric acid, and 2) an N-acetylated product of the aminoalcohol compound in hydrochloric acid or dilute sulfuric acid. 3) A method of esterifying in a large excess of concentrated sulfuric acid after hydrolysis, and 3) a method of reacting chlorosulfonic acid and an amino alcohol compound in N-methylpyrrolidone at 10 to 80 ° C.
[0003]
[Problems to be solved by the invention]
However, in the method of the above 1), it has the disadvantage that the operation for drying is required aliphatic amino alcohol compound of a raw material is cumbersome, in the above method 2), an aliphatic amino alcohol which is a raw material compounds of N- acetylated drying low extraction yields of the amino ester compound is a target compound on top necessary, both for industrial not be said to be advantageous. In the above method 3) , excess chlorosulfonic acid in the reaction solution is first decomposed with ice water, the solution obtained by the decomposition is neutralized, and then the aminoester compound is converted to N- from the neutralized solution. Not only is it necessary to extract with a suitable solvent other than methylpyrrolidone, but it is also necessary to recover N-methylpyrrolidone using a method such as distillation, which is not an industrially advantageous method. .
[0004]
[Means for Solving the Problems]
As a result of intensive studies on an industrially advantageous improved production method of amino ester compounds, the present inventors have obtained an amino alcohol compound or an N-acetylated product thereof, and a specific amount of sulfuric acid or fuming sulfuric acid with respect to these compounds. When the reaction is carried out while distilling off water or water and acetic acid as a by-product without using a reaction solvent such as an organic solvent under heating and reduced pressure conditions, the reaction can be performed without the need for complicated operations. And it discovered that the extraction yield of a reaction product improved remarkably, and came to complete this invention.
That is, the present invention is expressed in the form of free amine, 1.25 to 10-fold molar aminoalcohol compound (II) or its N- acetylated, the theoretical weight per hydroxyl group in these compounds A reaction product obtained by reacting with an amount of sulfuric acid or fuming sulfuric acid and reacting while distilling off water or water and acetic acid under reduced pressure conditions of 5 to 50 mmHg while heating in a range of 100 to 180 ° C. Is provided at a temperature of 80 to 150 ° C., and the product thus obtained is treated with water or ice to provide a process for producing an aminoester compound (I) in the form of a free amine. .
H-N (R 2) -W 2 -SO 2 CH 2 CH 2 OY (I)
H—N (R 1 ) —W 1 —SO 2 CH 2 CH 2 OH (II)
[Wherein W 1 may be substituted and may include —O— or —NR 3 — (wherein R 3 represents a hydrogen atom or a C 1 -C 4 alkyl group). A chain or branched C 2 -C 6 alkylene group is represented, and R 1 is a hydrogen atom, an optionally substituted C 1 -C 4 alkyl group, an optionally substituted phenyl group, or —W 1 —. The group represents SO 2 CH 2 CH 2 OY.
W 2 is a linear or branched C 2 -C 6 alkylene group which may be substituted and may contain —O— or —NR 3 — (R 3 represents the same meaning as described above). R 2 represents a hydrogen atom, an optionally substituted C 1 -C 4 alkyl group, an optionally substituted phenyl group, or a —W 2 —SO 2 CH 2 CH 2 OY group, and Y represents to display the -SO 3 H or an alkali metal or alkaline earth metal salt thereof. ]
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The amino alcohol compound (II) or N-acetylated product thereof may be a free amine or a mineral acid salt such as sulfate. These free amines and mineral acid salts can be used either in a water-containing state or in a dry state. In addition, the amino alcohol compound and its N-acetylated product may contain inorganic salts such as NaCl and Na 2 SO 4 . In the present invention, when the acetylated product of the amino alcohol compound is used as a starting material, it is necessary to remove acetic acid by-produced by hydrolysis of the acetylamino group out of the reaction system.
[0006]
The sulfuric acid concentration used in the reaction is not particularly limited, but is preferably adjusted to a concentration of 20 to 100%, more preferably 40 to 98%. When fuming sulfuric acid is used, its concentration is not particularly limited. Further , sulfuric acid and fuming sulfuric acid may be used in combination. The amount of sulfuric acid or fuming sulfuric acid used is, in terms of 100% sulfuric acid, 1.25 to 10 times the molar amount of the amino alcohol compound (II) or the theoretical amount per hydroxy group of the N-acetylated product, preferably Is a 1.25 to 5-fold molar amount. Therefore, when the amino alcohol compound (II) or N-acetylated product thereof has two or more hydroxy groups, the amount of sulfuric acid or fuming sulfuric acid used is the above (1.25 to 10-fold molar amount) x (hydroxy group). The number of
If the amount of sulfuric acid or fuming sulfuric acid used is less than 1.25 times the theoretical amount per hydroxy group, the reaction product has poor fluidity, making it difficult to extract the amino acid derivative and reducing the extraction yield. Tend to. On the other hand, if the amount of sulfuric acid or fuming sulfuric acid exceeds 10 times the theoretical amount per hydroxy group, the reaction rate tends to be slow.
[0007]
In the present invention, the order in which the amino alcohol compound (II) or an N-acetylated product thereof and sulfuric acid or fuming sulfuric acid are charged is not particularly limited.
The reaction temperature is generally higher from the viewpoint of the reaction rate, but side reactions occur at higher temperatures than necessary, and the yield of the aminoester compound (I) tends to decrease. 180 ° C. Degree of vacuum is set to allow the evaporation of the reaction system of water or water and acetic acid in the set reaction temperature, is 5～50MmHg. The water or water and acetic acid present in the reaction system are distilled off to the outside of the reaction system under heating and reduced pressure conditions, usually by stirring. The method of the present invention can be carried out by a batch method using an ordinary reactor such as a can, a tank and a kettle.
[0008]
Examples of the substituent of the linear or branched C 2 -C 6 alkylene group represented by W 1 in the general formula (II) include a halogen atom, a hydroxy group, a sulfate group, a carboxy group, a cyano group, and A sulfo group etc. are mentioned.
The substituent of the linear or branched C 2 -C 6 alkylene group represented by W 2 in the general formula (I) exists, for example, in the form of a halogen atom, an alkali metal or an alkaline earth metal salt. Examples thereof may include a sulfate group, a carboxy group which may be present in the form of an alkali metal or alkaline earth metal salt, a cyano group, and a sulfo group which may be present in the form of an alkali metal or alkaline earth metal salt. It is done.
Expressed in the form of the free amine, the aminoalcohol compound (II) can be obtained by a known method, for example by condensing the corresponding chloro or bromoalkylamine with mercaptoethanol and then oxidizing the resulting thioether compound with hydrogen peroxide . It is manufactured by the method to do. For amino alcohol compounds (II) N-acetylated, after acetylation thioether compound obtained in the condensation with acetic anhydride, prepared by the process of the resulting acetylated product is oxidized with hydrogen peroxide. Examples of the amino alcohol compound (II) and N-acetylated product thereof include the following compounds when expressed in the form of a free amine.
[0009]
H 2 NC 2 H 4 SO 2 C 2 H 4 OH
H 2 NC 3 H 6 SO 2 C 2 H 4 OH
H 2 NC 4 H 8 SO 2 C 2 H 4 OH
H 2 NC 5 H 10 SO 2 C 2 H 4 OH
H 2 NC 6 H 12 SO 2 C 2 H 4 OH
H 2 NC 2 H 4 OC 2 H 4 SO 2 C 2 H 4 OH
H 2 NC 2 H 4 OC 3 H 6 SO 2 C 2 H 4 OH
HN (C 2 H 4 SO 2 C 2 H 4 OH) 2
HN (CH 3 ) C 2 H 4 SO 2 C 2 H 4 OH
HN (C 2 H 5) C 2 H 4 SO 2 C 2 H 4 OH
HN (C 2 H 5) C 3 H 6 SO 2 C 2 H 4 OH
H 2 NCH (C 2 H 5 ) CH 2 SO 2 C 2 H 4 OH
H 2 NC 2 H 4 NHC 2 H 4 SO 2 C 2 H 4 OH
H 2 NC 2 H 4 NHCH (CH 3 ) CH 2 SO 2 C 2 H 4 OH
CH 3 CONHC 2 H 4 SO 2 C 2 H 4 OH
CH 3 CONHC 3 H 6 SO 2 C 2 H 4 OH
CH 3 CONHC 4 H 8 SO 2 C 2 H 4 OH
HN (C 6 H 5) -C 2 H 4 SO 2 C 2 H 4 OH
[0010]
The amino ester compound (I) is preferably taken out by treating the reaction product obtained after completion of the reaction with water or ice.
Specifically, for example, in ice water and cold water, or in ice water or cold water to which alkali such as sodium bicarbonate, potassium hydrogen carbonate, soda ash, potassium carbonate, sodium hydroxide and potassium hydroxide is added is preferable. Can be taken out in a liquid state by adding a reaction product kept at 80 to 150 ° C. When the reaction product is added to ice water or cold water and obtained in a liquid state, the alkali may be added to the obtained liquid. The amino ester compound (I) can also be isolated from these liquids by a known method such as concentration, lyophilization and filtration.
In particular, the aminoester compound (I) is preferably used after neutralization with an alkali for applications such as water and oil repellent finishing agents, silver halide photographic curing agents, and surfactants.
[0011]
【Example】
Next, the present invention will be described more specifically with reference to examples. Parts and% in the examples indicate parts by weight and% by weight, respectively.
[0012]
Example 1
After stirring 10.0 parts of 98% sulfuric acid and 70.8 parts of 25% N-ethyl- [2- (2-hydroxyethylsulfonyl) ethyl] amine sulfate aqueous solution with stirring, the pressure was reduced to 30 mmHg and the temperature was raised to 100 ° C. The reaction was continued at 100 ° C. while distilling off the water produced as a by-product to remove water from the reaction system. After completion of the reaction, the reaction product kept at 90 to 110 ° C. was poured into 100 parts of ice water, and the resulting aqueous solution was neutralized with soda ash to pH 1-2. The production rate of N-ethyl- [2- (2-sulfatoethylsulfonyl) ethyl] amine is 98%, and a small amount of N-ethyl- [2- (2-hydroxyethylsulfonyl) ethyl] amine sulfate Was included.
[0013]
Example 2
Even when 9.2 parts of 30% fuming sulfuric acid was used instead of 10.0 parts of 98% sulfuric acid, N-ethyl- [2- (2-sulfatoethylsulfonyl) ethyl] amine was produced in the same production rate as in Example 1. was gotten.
[0014]
Example 3
By stirring 16.8 parts of 98% sulfuric acid and 25.9 parts of aminopropyl-2-hydroxyethylsulfone sulfate under reduced pressure of 40 mmHg to 150 to 155 ° C. while distilling off the by-produced water. While removing water out of the reaction system, the reaction was continued at the same temperature to complete the reaction. After completion of the reaction, the reaction product kept at 120 to 130 ° C. was poured into 100 parts of ice water, and the resulting aqueous solution was neutralized with soda ash to pH 1-2. The production rate of aminopropyl-2-sulfate ethyl sulfone was 98%, and additionally contained a small amount of aminopropyl-2-hydroxyethyl sulfone sulfate.
[0015]
Example 4
A mixture of 336.8 parts of a 20% aqueous solution of bis- [2- (2-hydroxyethylsulfonyl) ethyl] amine sulfate, 5.0 parts of diatomaceous earth and 20.8 parts of 98% sulfuric acid was reduced to 50 mmHg with stirring. The reaction was continued at the same temperature after gradually raising the temperature to 110-120 ° C. while removing water out of the reaction system by distilling off the by-produced water. After completion of the reaction, the obtained reaction product was poured into 100 parts of ice water, and then neutralized with soda ash to pH 1-2. The yield of bis- [2- (2-sulfatoethylsulfonyl) ethyl] amine was 97%.
[0016]
Example 5
While stirring a mixture of 650 parts of a 30% aqueous solution of acetylaminoethyl-2-hydroxyethylsulfone and 150 parts of 98% sulfuric acid, the mixture was heated to 120 to 125 ° C. under reduced pressure of 50 mmHg, and acetic acid and water by-produced were distilled off. Thus, the reaction was continued at the same temperature while acetic acid and water were removed from the reaction system to complete the reaction. The obtained reaction product was poured into 500 parts of ice water and then neutralized with soda ash to pH 3-6. The production rate of aminoethyl-2-sulfate ethyl sulfone was 95%.
[0017]
Examples 6-10
When expressed in the form of a free amine in the same manner as in Example 3 except that an equimolar amount of the compound described in the second column of the following table was used instead of aminopropyl-2-hydroxyethylsulfone sulfate, The compounds described in column 3 were obtained in good yield.
[0018]
【The invention's effect】
According to the method of the present invention, an amino ester compound represented by the general formula (I) useful as an intermediate for various industrial products such as a water / oil repellent finish, a silver halide photographic curing agent, and a surfactant is industrially produced. In particular, it can be manufactured advantageously.
[0020]
Reference example 1
The neutralized aqueous solution obtained in Example 1 was freeze-dried to obtain solid N-ethyl- [2- (2-sulfatoethylsulfonyl) ethyl] amine in a yield of 97.5%.
This is reacted with polyfluoro-1-octanesulfonyl fluoride in the presence of triethylamine, and after completion of the reaction, alkali is added to form
C 8 F 17 SO 2 N ( C 2 H 5) C 2 H 4 SO 2 CH = CH 2
The water- and oil-repellent finishing agent (melting point: 123 to 125 ° C.) shown in FIG.
Claims (1)
Ｈ−Ｎ（Ｒ 2 ）−Ｗ 2 −ＳＯ 2 ＣＨ 2 ＣＨ 2 ＯＹ （Ｉ）
Ｈ−Ｎ（Ｒ 1 ）−Ｗ 1 −ＳＯ 2 ＣＨ 2 ＣＨ 2 ＯＨ （ＩＩ）
［式中、Ｗ 1 は置換されていてもよく、−Ｏ−又は−ＮＲ 3 −（ここで、Ｒ 3 は水素原子又はＣ 1 〜Ｃ 4 アルキル基を表す。）を含んでいてもよい直鎖状又は分枝状のＣ 2 〜Ｃ 6 アルキレン基を表し、Ｒ 1 は水素原子、置換されていてもよいＣ 1 〜Ｃ 4 アルキル基、置換されていてもよいフェニル基又は−Ｗ 1 −ＳＯ 2 ＣＨ 2 ＣＨ 2 ＯＨの基を表す。
Ｗ2は置換されていてもよく、−Ｏ−又は−ＮＲ3−（Ｒ3は前記と同じ意味を表す）を含んでいてもよい直鎖状又は分枝状のＣ2〜Ｃ6アルキレン基を表し、Ｒ2は水素原子、置換されていてもよいＣ1〜Ｃ4アルキル基、置換されていてもよいフェニル基又は−Ｗ2−ＳＯ2ＣＨ2ＣＨ2ＯＹの基を表し、Ｙは−ＳＯ3Ｈ又はそのアルカリ金属若しくはアルカリ土類金属塩を表す。］Expressed in the form of a free amine, aminoalcohol compound (II) or an N-acetylated product thereof is 1.25 to 10 times the molar amount of sulfuric acid or fuming sulfuric acid with respect to the theoretical amount per hydroxy group in these compounds. The reaction product obtained by the reaction is kept at 80 to 150 ° C. by heating to 100 to 180 ° C. and reacting while distilling off water or water and acetic acid under reduced pressure conditions of 5 to 50 mmHg . And a method for producing an aminoester compound (I) in the form of a free amine, characterized by treating the warmed product with water or ice .
H-N (R 2) -W 2 -SO 2 CH 2 CH 2 OY (I)
H—N (R 1 ) —W 1 —SO 2 CH 2 CH 2 OH (II)
[ Wherein W 1 may be substituted and may include —O— or —NR 3 — (wherein R 3 represents a hydrogen atom or a C 1 -C 4 alkyl group). Represents a chain or branched C 2 -C 6 alkylene group, R 1 represents a hydrogen atom, an optionally substituted C 1 -C 4 alkyl group, an optionally substituted phenyl group, or —W 1 —; Represents a SO 2 CH 2 CH 2 OH group.
W 2 is a linear or branched C 2 -C 6 alkylene group which may be substituted and may contain —O— or —NR 3 — (R 3 represents the same meaning as described above). R 2 represents a hydrogen atom, an optionally substituted C 1 -C 4 alkyl group, an optionally substituted phenyl group, or a —W 2 —SO 2 CH 2 CH 2 OY group, and Y represents —SO 3 H or an alkali metal or alkaline earth metal salt thereof. ]
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|---|---|---|---|
| JP33863395A JP3735914B2 (en) | 1995-12-26 | 1995-12-26 | Method for producing aminoester compound |
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| JP33863395A JP3735914B2 (en) | 1995-12-26 | 1995-12-26 | Method for producing aminoester compound |
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