JPH0565253A - Method for producing amino acid amino alkyl ester - Google Patents
Method for producing amino acid amino alkyl esterInfo
- Publication number
- JPH0565253A JPH0565253A JP3227888A JP22788891A JPH0565253A JP H0565253 A JPH0565253 A JP H0565253A JP 3227888 A JP3227888 A JP 3227888A JP 22788891 A JP22788891 A JP 22788891A JP H0565253 A JPH0565253 A JP H0565253A
- Authority
- JP
- Japan
- Prior art keywords
- amino acid
- hydrochloride
- amino
- reaction
- hydrogen chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 amino acid hydrochloride Chemical class 0.000 claims abstract description 20
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 abstract description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001413 amino acids Chemical class 0.000 abstract description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004471 Glycine Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 235000001014 amino acid Nutrition 0.000 description 17
- 229940024606 amino acid Drugs 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 150000003951 lactams Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OQEBBZSWEGYTPG-UHFFFAOYSA-N 3-aminobutanoic acid Chemical compound CC(N)CC(O)=O OQEBBZSWEGYTPG-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JBBURJFZIMRPCZ-XRIGFGBMSA-N (2s)-2,6-diaminohexanoic acid;hydron;dichloride Chemical compound Cl.Cl.NCCCC[C@H](N)C(O)=O JBBURJFZIMRPCZ-XRIGFGBMSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- PQMCFTMVQORYJC-UHFFFAOYSA-N 2-aminocyclohexan-1-ol Chemical compound NC1CCCCC1O PQMCFTMVQORYJC-UHFFFAOYSA-N 0.000 description 1
- QLJYMWXTQLANPB-UHFFFAOYSA-N 2-aminoethyl hexanoate Chemical compound CCCCCC(=O)OCCN QLJYMWXTQLANPB-UHFFFAOYSA-N 0.000 description 1
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- DPURNAQARVHQHE-UHFFFAOYSA-N 4-aminobutane-1,2,3-tricarboxylic acid Chemical compound NCC(C(O)=O)C(C(O)=O)CC(O)=O DPURNAQARVHQHE-UHFFFAOYSA-N 0.000 description 1
- DRNGLYHKYPNTEA-UHFFFAOYSA-N 4-azaniumylcyclohexane-1-carboxylate Chemical compound NC1CCC(C(O)=O)CC1 DRNGLYHKYPNTEA-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- VUPSBXWCGBAYBD-UHFFFAOYSA-N CCCCCC(=O)OCC(N)(N)N Chemical compound CCCCCC(=O)OCC(N)(N)N VUPSBXWCGBAYBD-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- DWPCPZJAHOETAG-IMJSIDKUSA-N L-lanthionine Chemical compound OC(=O)[C@@H](N)CSC[C@H](N)C(O)=O DWPCPZJAHOETAG-IMJSIDKUSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940073579 ethanolamine hydrochloride Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229960003646 lysine Drugs 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 229960005337 lysine hydrochloride Drugs 0.000 description 1
- DWPCPZJAHOETAG-UHFFFAOYSA-N meso-lanthionine Natural products OC(=O)C(N)CSCC(N)C(O)=O DWPCPZJAHOETAG-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアミノ酸アミノアルキル
エステルの製造法に関する。アミノ酸アミノエステルは
ポリウレタンの原料であるイソシアネートの原料として
用いられる。The present invention relates to a method for producing amino acid aminoalkyl esters. Amino acid amino ester is used as a raw material for isocyanate, which is a raw material for polyurethane.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】アミノ
酸アミノアルキルエステルの製造法としては例えば次の
方法が知られている。 （１）有機酸またはアミノ酸の塩酸塩とアミノアルコー
ル塩酸塩とのエステル化反応に際し、有機溶剤を共存せ
しめた反応系内に塩化水素ガスを通じながら加熱還流さ
せ、生成した水を塩酸として連続的に留去しながらエス
テル化反応を進める方法が知られている（特公昭４５−
１４７７１号公報、同４６−３５２４６号公報）。この
方法は、常圧でエステル化反応を行っており、反応初期
においては反応が比較的順調に進行するが、次第に反応
速度が低下し、収率の低い方法である。 （２）アミノ酸塩酸塩とアミノアルコール塩酸塩とを加
熱しエステル化を行なうに際し、水と共沸混合物をつく
る有機溶剤の非存在下に塩化水素ガスを反応系に吸収さ
せて反応させる方法が知られている（特公昭５９−４５
６６７号公報）。この方法は、反応一脱水を５〜６回繰
り返す煩雑な作業を行い７５〜８０％の収率を得ている
が、１０mmHg以下という高真空を必要とする方法であ
る。 （３）アミノ酸塩酸塩とアミノアルコール塩酸塩とのエ
ステル化反応を、有機溶剤を共存せしめた反応系内に塩
化水素ガスを通じながら加熱還流することによって行な
うに際し、反応液中に界面活性剤を添加する方法が知ら
れている（特公昭60−７９７８号公報）。2. Description of the Related Art For example, the following methods are known as methods for producing amino acid aminoalkyl esters. (1) In the esterification reaction of an organic acid or amino acid hydrochloride and an aminoalcohol hydrochloride, the reaction system in the presence of an organic solvent is heated to reflux while passing hydrogen chloride gas, and the generated water is continuously converted to hydrochloric acid. A method is known in which the esterification reaction proceeds while distilling off (Japanese Patent Publication No. 45-
14771 and 46-35246). In this method, the esterification reaction is carried out under normal pressure, and the reaction proceeds relatively smoothly in the initial stage of the reaction, but the reaction rate gradually decreases and the yield is low. (2) A method is known in which, when an amino acid hydrochloride and an aminoalcohol hydrochloride are heated for esterification, hydrogen chloride gas is absorbed in the reaction system in the absence of an organic solvent that forms an azeotropic mixture with water and the reaction is performed. It has been (Japanese Patent Publication Sho 59-45)
667). This method is a method that requires a high vacuum of 10 mmHg or less, though a complicated work of repeating reaction and dehydration 5 to 6 times is performed to obtain a yield of 75 to 80%. (3) When the esterification reaction of amino acid hydrochloride and aminoalcohol hydrochloride is carried out by heating under reflux while passing hydrogen chloride gas into a reaction system in the presence of an organic solvent, a surfactant is added to the reaction solution. A method of doing so is known (Japanese Patent Publication No. 60-7978).
【０００３】この方法は長時間の反応時間が必要であ
り、また反応終了後には、加えた界面活性剤を除去する
工程が必要になり、工業的に有利な方法とはいえない。 （４）リジン・二塩酸塩とエタノールアミン・塩酸塩と
をエステル化反応させ、2,6,２' −トリアミノエチルヘ
キサノエート・三塩酸塩を製造する方法において、触媒
として塩化水素を供給し反応物に塩化水素を吸収させる
吸収装置、反応物を反応させる反応器および反応物から
水分を除去する脱水装置を設け、反応物を吸収装置、反
応器、脱水装置の順に循環させる方法が知られている
（特開昭６１−５３２４８号公報）。This method requires a long reaction time and, after the completion of the reaction, requires a step of removing the added surfactant, which is not an industrially advantageous method. (4) a lysine dihydrochloride and ethanolamine hydrochloride reacted esterification, 2,6,2 '- supplying a process for preparing a tri-aminoethyl hexanoate · trihydrochloride, hydrogen chloride as a catalyst A method is known in which an absorption device for absorbing hydrogen chloride in the reaction product, a reactor for reacting the reaction product, and a dehydration device for removing water from the reaction product are provided, and the reaction product is circulated in the order of the absorption device, the reactor, and the dehydration device. (JP-A 61-53248).
【０００４】この方法は、塩化水素吸収装置・反応器・
脱水装置の間を反応液を循環させる複雑な操作が必要で
あり、また、各装置の条件（反応温度、反応圧力）が異
なっており操作が難しい。煩雑な作業や高真空を必要と
せず、また特殊な添加物を加えることなく、短い反応時
間で十分な反応率で、しかも簡単な操作で工業的に有利
なアミノ酸アミノアルキルエステルを製造する方法が求
められている。This method is applied to a hydrogen chloride absorption device / reactor /
A complicated operation is required to circulate the reaction liquid between the dehydrating devices, and the conditions (reaction temperature, reaction pressure) of each device are different, which makes the operation difficult. A method of producing an industrially advantageous amino acid aminoalkyl ester with a short reaction time, a sufficient reaction rate, and a simple operation, without requiring complicated work or high vacuum and without adding a special additive. It has been demanded.
【０００５】[0005]
【課題を解決するための手段】本発明はアミノ酸塩酸塩
とアミノアルコール塩酸塩とを塩化水素ガスを通じなが
ら、５０〜４００mmHgの減圧下で反応させることを特徴
とするアミノ酸アミノアルキルエステルの製造法に関す
る。アミノ酸塩酸塩は、少なくとも１個のアミノ基と少
なくとも１個のカルボキシル基とを持つ、炭素原子数２
〜18個の脂肪族もしくは芳香族アミノ酸、または３〜12
員環のラクタムの塩酸塩である。特に好ましく用いられ
るアミノ酸は、脂肪族のモノアミノモノカルボン酸、ジ
アミノモノカルボン酸、モノアミノジカルボン酸、ジア
ミノジカルボン酸などである。これらのアミノ酸が環化
して形成するラクタムもまた好ましく用いられる。上記
化合物の具体例としては、グリシン、３−アミノプロピ
オン酸、ω−アミノカプロン酸、ω−アミノラウリン
酸、アラニン、イソロイシン、３−アミノ酪酸、４−ア
ミノシクロヘキサンカルボン酸、フェニルアラニン、メ
チオニン、アミノ安息香酸、アスパラギン酸、グルタミ
ン酸、リジン、ランチオニン、１−アミノ−２・３・４
−ブタントリカルボン酸、上記アミノ酸のラクタム、ピ
ロリドン、カプロラクタム、ラウロラクタムなどが挙げ
られる。The present invention relates to a method for producing an amino acid aminoalkyl ester, which comprises reacting an amino acid hydrochloride and an aminoalcohol hydrochloride with hydrogen chloride gas under a reduced pressure of 50 to 400 mmHg. .. Amino acid hydrochloride has 2 carbon atoms and has at least one amino group and at least one carboxyl group.
~ 18 aliphatic or aromatic amino acids, or 3-12
It is a lactam hydrochloride with a member ring. Particularly preferably used amino acids are aliphatic monoaminomonocarboxylic acids, diaminomonocarboxylic acids, monoaminodicarboxylic acids and diaminodicarboxylic acids. A lactam formed by cyclizing these amino acids is also preferably used. Specific examples of the above compounds include glycine, 3-aminopropionic acid, ω-aminocaproic acid, ω-aminolauric acid, alanine, isoleucine, 3-aminobutyric acid, 4-aminocyclohexanecarboxylic acid, phenylalanine, methionine and aminobenzoic acid. , Aspartic acid, glutamic acid, lysine, lanthionine, 1-amino-2.3.4
-Butanetricarboxylic acid, lactams of the above amino acids, pyrrolidone, caprolactam, laurolactam and the like.
【０００６】アミノアルコール塩酸塩は、１個の第一も
しくは第二水酸基および１個の第一アミノ基を有する炭
素原子２〜１２個のアミノアルコールの塩酸塩である。
上記アミノアルコールは、そのアルキレン連鎖中に酸
素、硫黄などの複素原子を含んだものや、エステル化反
応に対して不活性な基、例えばニトロ、ハロゲン、アル
キル、フェニル基などの置換基を含むものであってもよ
い。アミノアルコールの具体例としては、エタノールア
ミン、１−アミノ−２−プロパノール、２−アミノ−１
−プロパノール、２−アミノイソブタノール、２−アミ
ノ−１−ブタノール、２−（２−アミノエトキシ）−エ
タノール、２−アミノシクロヘキサノールなどが挙げら
れる。Amino alcohol hydrochloride is a hydrochloride salt of an amino alcohol having 2 to 12 carbon atoms, which has one primary or secondary hydroxyl group and one primary amino group.
The above amino alcohols include those having a hetero atom such as oxygen and sulfur in the alkylene chain, and those having a group inert to the esterification reaction, for example, a substituent such as nitro, halogen, alkyl and phenyl groups. May be Specific examples of amino alcohols include ethanolamine, 1-amino-2-propanol, and 2-amino-1.
-Propanol, 2-aminoisobutanol, 2-amino-1-butanol, 2- (2-aminoethoxy) -ethanol, 2-aminocyclohexanol and the like.
【０００７】アミノ酸塩酸塩とアミノアルコール塩酸塩
とのモル比は１：0.8 〜５、好ましくは１：1.２〜3.０
である。用いる塩化水素ガスの量はアミノ酸塩酸塩１モ
ル当り毎分５０〜１０００ml（常温常圧換算）である。
反応は５０〜４００mmHg、好ましくは６０〜３１０mmHg
減圧下、５０〜１６０℃で３〜２０時間行われる。The molar ratio of amino acid hydrochloride to amino alcohol hydrochloride is 1: 0.8-5, preferably 1: 1.2-3.0.
Is. The amount of hydrogen chloride gas used is 50 to 1000 ml / min (converted to normal temperature and atmospheric pressure) per mol of amino acid hydrochloride.
The reaction is 50 to 400 mmHg, preferably 60 to 310 mmHg
It is carried out under reduced pressure at 50 to 160 ° C. for 3 to 20 hours.
【０００８】５０mmHg以上の強い減圧状態とするために
は、大きな能力の減圧装置が必要となるし、また、操作
性や塩化水素ガスの回収にも問題を生じる。４００mmHg
以下の弱い減圧状態では反応操作は容易になるが、反応
速度即ち反応率が低下してしまう。反応物から目的物の
単離は、例えば反応液を冷却した後、溶媒を加え晶析す
ることにより行われる。In order to obtain a strong depressurized state of 50 mmHg or more, a depressurizing device having a large capacity is required, and there is a problem in operability and recovery of hydrogen chloride gas. 400 mmHg
In the following weak depressurized state, the reaction operation becomes easy, but the reaction rate, that is, the reaction rate, decreases. Isolation of the desired product from the reaction product is performed, for example, by cooling the reaction solution and then adding a solvent to crystallize.
【０００９】[0009]
【実施例】以下に実施例及び対照例を示す。EXAMPLES Examples and comparative examples will be shown below.
【００１０】実施例１ 攪拌器、温度計、ガス導入管、液滴下管、およびト字管
をかいしてのリービッヒ凝縮器付きの五つ口丸底フラス
コにエタノールアミン１８３ｇ（３モル）を投入した。
塩化水素ガスをガス導入管中に通過させてエタノールア
ミン全部をその塩酸塩に転換してから、リジン１塩酸塩
２７４ｇ（1.５モル）を添加した。８０〜１２０℃の温
度で塩化水素ガスをガス導入管中に通過させてリジン塩
酸塩に転換させた。Example 1 183 g (3 mol) of ethanolamine was placed in a five-necked round bottom flask equipped with a Liebig condenser equipped with a stirrer, a thermometer, a gas inlet tube, a liquid drop tube, and a T-shaped tube. did.
Hydrogen chloride gas was passed through the gas inlet tube to convert all of the ethanolamine to its hydrochloride salt, and then 274 g (1.5 mol) of lysine monohydrochloride was added. Hydrogen chloride gas was passed through a gas inlet tube at a temperature of 80-120 ° C to convert it to lysine hydrochloride.
【００１１】さらに、塩化水素ガスを毎分３００ml（常
温常圧換算）の割合で通過させ、反応混合物を１２０℃
に加熱し、水流ポンプを用いて１５０mmHg（絶対）まで
徐々に減圧した。留出した水はリービッヒ凝縮器で凝縮
した。反応液をサンプリングし高速液体クロマトグラフ
により分析した。目的物の反応率は、反応７時間で８２
％、１０時間で８６％であった。反応後、塩化水素の供
給を止め、窒素を用いて常圧に戻した後、６０℃まで冷
却した。これにメタノール１０８０ｇおよびｏ−ジクロ
ルベンゼン７２０ｇの混合液を加えて溶解した後、少量
の種晶を加えて晶析した。結晶を濾別し、晶析時と同一
組成のメタノール／ｏ−ジクロルベンゼン混合液を用い
て結晶を洗浄し、濾別した。Further, hydrogen chloride gas was passed through at a rate of 300 ml / min (converted at room temperature and atmospheric pressure), and the reaction mixture was heated at 120 ° C.
Then, the pressure was gradually reduced to 150 mmHg (absolute) using a water pump. The distilled water was condensed by the Liebig condenser. The reaction solution was sampled and analyzed by high performance liquid chromatography. The reaction rate of the target compound is 82 after 7 hours of reaction.
% Was 86% in 10 hours. After the reaction, the supply of hydrogen chloride was stopped, the pressure was returned to normal pressure using nitrogen, and then the temperature was cooled to 60 ° C. A mixed solution of 1080 g of methanol and 720 g of o-dichlorobenzene was added to and dissolved in the solution, and a small amount of seed crystals were added for crystallization. The crystals were separated by filtration, washed with a methanol / o-dichlorobenzene mixed solution having the same composition as at the time of crystallization, and separated by filtration.
【００１２】この湿結晶を減圧乾燥器を用いて、５mmH
g、１００℃で８時間乾燥した。淡黄白色の固体２９４
ｇを得た。顕微鏡観察で５×３０ミクロン程度の針状晶
（融点：１７３℃）であり、液体クロマトグラフィーを
用いた分析により、目的の2, 6, ２' −トリアミノエチ
ルヘキサノエート・三塩酸塩の含有量は９7.１％であっ
た。晶析を含めた収率は６４％であった。This wet crystal was dried at 5 mmH using a vacuum dryer.
g, dried at 100 ° C. for 8 hours. Pale yellowish white solid 294
g was obtained. Needles of about 5 × 30 microns by microscopic observation (mp: 173 ° C.) are, by analysis using liquid chromatography, another object, 6, 2 '- birds aminoethyl hexanoate · trihydrochloride The content was 97.1%. The yield including crystallization was 64%.
【００１３】実施例２ 実施例１において、塩化水素ガスの流量を毎分１００ml
（常温常圧換算）に代える以外は実施例１と同様に行い
反応液を得た。実施例１と同様に分析した結果、目的物
の反応率は反応７時間で７１％、１０時間で７９％であ
った。Example 2 In Example 1, the flow rate of hydrogen chloride gas was 100 ml / min.
A reaction liquid was obtained in the same manner as in Example 1 except that the temperature was changed to room temperature and atmospheric pressure. As a result of analysis in the same manner as in Example 1, the reaction rate of the target product was 71% after 7 hours of reaction and 79% after 10 hours.
【００１４】実施例３および４並びに対照例１および２ 実施例１において、反応圧力を第１表に示す反応圧力に
する以外は実施例１と同様に行い反応液を得た。実施例
１と同様に分析した結果、第１表に示す反応率を得た。Examples 3 and 4 and Comparative Examples 1 and 2 A reaction solution was obtained in the same manner as in Example 1 except that the reaction pressures shown in Table 1 were used. As a result of the same analysis as in Example 1, the reaction rates shown in Table 1 were obtained.
【００１５】[0015]
【表１】 [Table 1]
【００１６】表から明らかな如く、本発明は対照に比べ
て高反応率で目的物を得ることができる。As is apparent from the table, the present invention can obtain the desired product at a higher reaction rate than the control.
【００１７】[0017]
【発明の効果】本発明の方法によりアミノ酸アミノアル
キルエステルを収率よく工業的に安価に製造することが
できる。INDUSTRIAL APPLICABILITY By the method of the present invention, amino acid aminoalkyl ester can be produced in good yield and industrially at low cost.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ (72)発明者 久保田 善康 千葉県市原市五井南海岸11−１ 協和油化 株式会社千葉工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location // C07B 61/00 300 (72) Inventor Yoshiyasu Kubota 11-1 Goi Minamikaigan, Ichihara-shi, Chiba Kyowa Yuka Co., Ltd. Chiba factory
Claims (1)
塩とを塩化水素ガスを通じながら、５０〜４００mmHgの
減圧下で反応させることを特徴とするアミノ酸アミノア
ルキルエステルの製造法。1. A process for producing an amino acid aminoalkyl ester, which comprises reacting an amino acid hydrochloride with an amino alcohol hydrochloride under a reduced pressure of 50 to 400 mmHg while passing hydrogen chloride gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22788891A JP3160321B2 (en) | 1991-09-09 | 1991-09-09 | Method for producing amino acid aminoalkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22788891A JP3160321B2 (en) | 1991-09-09 | 1991-09-09 | Method for producing amino acid aminoalkyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0565253A true JPH0565253A (en) | 1993-03-19 |
| JP3160321B2 JP3160321B2 (en) | 2001-04-25 |
Family
ID=16867906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22788891A Expired - Fee Related JP3160321B2 (en) | 1991-09-09 | 1991-09-09 | Method for producing amino acid aminoalkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3160321B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10968168B2 (en) | 2017-05-15 | 2021-04-06 | Asahi Kasei Kabushiki Kaisha | Isocyanate production method |
-
1991
- 1991-09-09 JP JP22788891A patent/JP3160321B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10968168B2 (en) | 2017-05-15 | 2021-04-06 | Asahi Kasei Kabushiki Kaisha | Isocyanate production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3160321B2 (en) | 2001-04-25 |
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