WO2002102762A1 - Nouveau procede de preparation d'hydroxyarylglycines, d'alcoxyarylglycines et de leurs glycinates - Google Patents

Nouveau procede de preparation d'hydroxyarylglycines, d'alcoxyarylglycines et de leurs glycinates Download PDF

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Publication number
WO2002102762A1
WO2002102762A1 PCT/ES2002/000300 ES0200300W WO02102762A1 WO 2002102762 A1 WO2002102762 A1 WO 2002102762A1 ES 0200300 W ES0200300 W ES 0200300W WO 02102762 A1 WO02102762 A1 WO 02102762A1
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WO
WIPO (PCT)
Prior art keywords
reaction
catalyst
cyanide
nitrile
hydrogenolysis
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.)
Ceased
Application number
PCT/ES2002/000300
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English (en)
Spanish (es)
Inventor
Miguel Angel Sierra Rodriguez
Mar Gomez Gallego
Roberto Alcazar Montero
Pedro Ramirez Lopez
Javier Moreno Lozano
Juan José LUCENA MAROTTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidad Complutense de Madrid
Universidad Autonoma de Madrid
Original Assignee
Universidad Complutense de Madrid
Universidad Autonoma de Madrid
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Filing date
Publication date
Application filed by Universidad Complutense de Madrid, Universidad Autonoma de Madrid filed Critical Universidad Complutense de Madrid
Publication of WO2002102762A1 publication Critical patent/WO2002102762A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton

Definitions

  • the present invention falls within the field of the synthesis of ⁇ -amino acids, and their amino esters, all of them of interest to the pharmaceutical and agrochemical industry.
  • hydroxyarylglycins are especially interesting.
  • 2-hydroxyphenylglycine is used in the manufacture of agrochemicals and 4-hydroxyphenylglycine is used as a precursor in the manufacture of cephalosporins (amoxicillin, cefadroxil) [GO 2,522,998] [GO 2,540,523] [EP-A-0 474 112], [EP 47,014], [EP 53 276] and as raw material to obtain 4-hydroxybenzyl cyanide.
  • the present invention consists of a new process that allows the synthesis of 2 and 4-hydroxy or alkoxyphenylglycins distinctly substituted in the aromatic ring, and of their glycinates (1,), with a high degree of purity and with good yields.
  • the starting imines are obtained quantitatively by reaction between equimolecular amounts of the corresponding hydroxy- or alkoxybenzaldehyde and rjenzylamine, at reflux of ethanol.
  • the synthesis of ⁇ -aminonitriles is carried out with quantitative yields by using reagents that prevent the generation of hydrocyanic acid (HCN) in the reaction medium, which avoids the problems arising from the latter's high toxicity and risks. which involve both the handling of liquid HCN and the generation in situ of this reagent from one of its salts.
  • HCN hydrocyanic acid
  • the described method, object of the present invention allows to obtain indistinctly, 2- and 4-hydroxy or 2- and 4-alkoxyarylglycins and their methyl or ethyl esters, and competes for their versatility, simplicity and performance with those previously collected in literature.
  • TMSCN trimethylsilyl cyanide
  • Pd (c) (15% by weight of Pd (C) with respect to the mass of the substrate) is added to a solution of the N-benzylamine ester in ethanol and then subjected to hydrogen pressure (50 psi ) for 16 hours.
  • the crude is filtered and the solvent is removed under reduced pressure, obtaining ethyl 2-hydroxyphenylglycinate in 93% yield, in the form of a yellow oil.
  • Phenylglycinates are stable for short periods of time at room temperature, so it is convenient to store them in the form of hydrochlorides. For this, the phenylglycinate is dissolved in ether and then a stream of HCl (g) is bubbled through the solution until precipitation.
  • Example 2 2-hydroxyphenylglycine
  • Example 3 methyl 2-methoxyphenyl glycinate As in Example 1, using 2-methoxybenzaldehyde and benzylamine as the starting product. Obtaining nitrile from imine is carried out using an imine: TMSCN molar ratio of 1: 1.5. The nitrile alcoholysis is carried out in methanol. After hydrogenation, methyl 2-methoxyphenylglycinate is obtained in 77% yield.
  • Example 2 As in Example 1, using 2- isopropoxybenzaldehyde and benzylamine as the starting product. After hydrogenation, ethyl 2-isopropoxyphenyl glycinate is obtained in 86% yield.
  • Example 6 methyl 4-methoxyphenyl glycinate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un nouveau procédé de synthèse d'hydroxyarylglycines, d'alcoxyarylglycines et de leurs glycinates, chimiquement pures, avec des bons rendements. Ces composés sont de bons précurseurs pour l'obtention de produits pharmaceutiques et agrochimiques.
PCT/ES2002/000300 2001-06-14 2002-06-14 Nouveau procede de preparation d'hydroxyarylglycines, d'alcoxyarylglycines et de leurs glycinates Ceased WO2002102762A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200101385A ES2183718B2 (es) 2001-06-14 2001-06-14 Nuevo procedimiento para la preparacion de hidroxiarilglicinas, alcoxiarilglicinas y sus glicinatos.
ESP200101385 2001-06-14

Publications (1)

Publication Number Publication Date
WO2002102762A1 true WO2002102762A1 (fr) 2002-12-27

Family

ID=8498068

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2002/000300 Ceased WO2002102762A1 (fr) 2001-06-14 2002-06-14 Nouveau procede de preparation d'hydroxyarylglycines, d'alcoxyarylglycines et de leurs glycinates

Country Status (2)

Country Link
ES (1) ES2183718B2 (fr)
WO (1) WO2002102762A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722488A (zh) * 2018-05-04 2018-11-02 江苏师范大学 一种增强路易斯酸性的双金属中心金属-有机框架材料及其制备方法
CN110194721A (zh) * 2019-06-06 2019-09-03 浙江工业大学 一种羟基苯甘氨酸离心母液处理装置及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1339053A (en) * 1970-05-04 1973-11-28 Astra Laekemedel Ab Method for the preparation of aromatic a-amino acids and intermediates therefor
GB1388341A (en) * 1972-08-11 1975-03-26 Chinoin Gyogyszer Es Vegyeszet Starting material and process for the preparation of d- - 2- amino-2-p-hydroxyphenyl- acetic acid
EP0807621A1 (fr) * 1996-05-13 1997-11-19 Lilly Industries Limited Dérivés de phénylglycine et leur utilisation comme agent thérapeutique
EP0839799A1 (fr) * 1995-05-19 1998-05-06 Kissei Pharmaceutical Co., Ltd. Derives de 2-hydroxyphenylalkylamine et inhibiteurs de la reaction de maillard
PL179271B1 (pl) * 1995-12-12 2000-08-31 Politechnika Wroclawska Sposób wytwarzania kwasów 2-aminoalkanowych

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1339053A (en) * 1970-05-04 1973-11-28 Astra Laekemedel Ab Method for the preparation of aromatic a-amino acids and intermediates therefor
GB1388341A (en) * 1972-08-11 1975-03-26 Chinoin Gyogyszer Es Vegyeszet Starting material and process for the preparation of d- - 2- amino-2-p-hydroxyphenyl- acetic acid
EP0839799A1 (fr) * 1995-05-19 1998-05-06 Kissei Pharmaceutical Co., Ltd. Derives de 2-hydroxyphenylalkylamine et inhibiteurs de la reaction de maillard
PL179271B1 (pl) * 1995-12-12 2000-08-31 Politechnika Wroclawska Sposób wytwarzania kwasów 2-aminoalkanowych
EP0807621A1 (fr) * 1996-05-13 1997-11-19 Lilly Industries Limited Dérivés de phénylglycine et leur utilisation comme agent thérapeutique

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] accession no. STN Database accession no. 2001:557778 *
DATABASE CAPLUS [online] LEBLANC ET AL.: "Synthesis of alpha-aminonitriles by self-catalyzed, stoichiometric reaction of primary amines, aldehydes and trimethylsilyl cyanide", accession no. STN Database accession no. 1993:21997 *
TETRAHEDRON LETTERS, vol. 33, 1992, pages 6295 - 6298 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722488A (zh) * 2018-05-04 2018-11-02 江苏师范大学 一种增强路易斯酸性的双金属中心金属-有机框架材料及其制备方法
CN108722488B (zh) * 2018-05-04 2021-02-12 江苏师范大学 一种增强路易斯酸性的双金属中心金属-有机框架材料及其制备方法
CN110194721A (zh) * 2019-06-06 2019-09-03 浙江工业大学 一种羟基苯甘氨酸离心母液处理装置及方法
CN110194721B (zh) * 2019-06-06 2022-05-24 浙江工业大学 一种羟基苯甘氨酸离心母液处理装置及方法

Also Published As

Publication number Publication date
ES2183718B2 (es) 2004-03-16
ES2183718A1 (es) 2003-03-16

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