96562-58-2

Basic information

• Product Name: Methyl (R)-(+)-2-(4-hydroxyphenoxy)propanoate
• Synonyms: METHYL-[(R)-(+)-2-(4-HYDROXYPHENOXY)-PROPANOAT];METHYL (R)-(+)-2-(4-HYDROXYPHENOXY)PROPANOATE;METHYL (R)-(+)-2-(4-HYDROXYPHENOXY)PROPIONATE;METHYL R-2-(4-HYDROXYPHENOXY)PROPIONATE;METHYL D-2-(4-HYDROXYPHENOXY) PROPIONATE;D-MHPP;AURORA KA-6234;(R)-(+)-2-(4-HYDROXYPHENOXY)PROPIONIC ACID METHYL ESTER
• CAS NO: 96562-58-2
• Molecular Formula: C₁₀H₁₂O₄
• Molecular Weight: 196.2
• EINECS: 411-950-4
• Product Categories: Aromatic Propionic Acids;Heterocyclic Compounds;API intermediates;CHIRAL COMPOUNDS;Chiral Building Blocks;Esters;Organic Building Blocks
• Mol File: 96562-58-2.mol
• Article Data: 6

Chemical Properties

• Melting Point: 64-67 °C(lit.)
• Boiling Point: 313.4 °C at 760 mmHg
• Flash Point: 121.6 °C
• Appearance: /
• Density: 1.187 g/cm³
• Vapor Pressure: 0.000271mmHg at 25°C
• Refractive Index: 42.5 ° (C=1, CHCl3)
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: 9320 in mg/100g standard fat at 20 ℃
• PKA: 10.07±0.15(Predicted)
• Water Solubility: 13.46g/L at 20℃
• CAS DataBase Reference: Methyl (R)-(+)-2-(4-hydroxyphenoxy)propanoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl (R)-(+)-2-(4-hydroxyphenoxy)propanoate(96562-58-2)
• EPA Substance Registry System: Methyl (R)-(+)-2-(4-hydroxyphenoxy)propanoate(96562-58-2)

Safety Data

• Hazard Codes: Xi
• Statements: 41-52/53
• Safety Statements: 26-39-61
• WGK Germany: 2
• Hazardous Substances Data: 96562-58-2(Hazardous Substances Data)

Usage

Flammability and Explosibility

Notclassified

InChI:InChI=1/C10H12O4/c1-7(10(12)13-2)14-9-5-3-8(11)4-6-9/h3-7,11H,1-2H3/t7-/m1/s1

Synthetic route

methanol (67-56-1) + (R)-2-(4-hydroxyphenoxy)propionic acid (94050-90-5) → (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
With catalyst prepared from tetra-N-propyl zirconate, n-propanol, r-Al2O3, H2PtCl6, and (NH4)2SO4 In toluene at 110℃; for 2h; Reagent/catalyst;	95.2%
With sulfuric acid In toluene at 70℃; for 3h;	90%

methyl-(S)-2-chloropropionate (73246-45-4) + hydroquinone (123-31-9) → (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 80 - 90℃; for 3h; Temperature;	95%

methyl (2S)-2-bromopropanoate (20047-41-0, 57885-43-5, 5445-17-0, 62076-23-7) + hydroquinone (123-31-9) → (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 80 - 90℃; for 3h;	95%

(RS)-methyl 2-(4-hydroxyphenoxy)propionate (60075-04-9) → (S)-(-)-2-(4-hydroxyphenoxy)propionic acid (105118-15-8) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
With Aspergillus oryzae WZ007; sodium hydroxide In water at 35℃; pH=7; Enzymatic reaction;	A 86.5% B 88.4%
With lyophilized mycelium of Aspergillus oryzae WZ007 In aq. phosphate buffer at 30℃; pH=8; Enzymatic reaction; enantioselective reaction;	A n/a B n/a

methyl (R)-2-(4-acetoxyphenoxy)propionate (111842-06-9) → (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
With hydrogenchloride In methanol	96% (94-95% enantiomeric excess)

hydroquinone (123-31-9) → (S)-(-)-2-(4-hydroxyphenoxy)propionic acid (105118-15-8) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium hydroxide / dimethyl sulfoxide / 0 - 30 °C / Inert atmosphere 2: lyophilized mycelium of Aspergillus oryzae WZ007 / aq. phosphate buffer / 30 °C / pH 8 / Enzymatic reaction View Scheme
Multi-step reaction with 2 steps 1.1: sodium sulfite; sodium methylate / methanol / 0.5 h / 30 °C / Inert atmosphere 1.2: 6 h / Inert atmosphere 2.1: Aspergillus oryzae WZ007; sodium hydroxide / water / 35 °C / pH 7 / Enzymatic reaction View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → (R)-2-(4-hydroxyphenoxy)propionic acid (94050-90-5)

Conditions	Yield
With sodium hydroxide In water at 20℃; for 3h;	92.3%

1,3-benzodioxol-5-ylmethyl amine (2620-50-0) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → N-benzo[1,3]dioxol-5-ylmethyl-2-(4-hydroxy-phenoxy)-propionamide

Conditions	Yield
for 4.5h; Heating;	87%

2-iodophenylamine (615-43-0) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → (R)-2-(4-hydroxyphenoxy)-N-(2-iodophenyl)propanamide

Conditions	Yield
Stage #1: 2-iodophenylamine With diisobutylaluminium hydride In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere; Stage #2: (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester In tetrahydrofuran; hexane at 0 - 20℃; for 12h; Inert atmosphere;	87%
Stage #1: 2-iodophenylamine With diisobutylaluminium hydride In tetrahydrofuran; hexane at 0℃; for 0.5h; Inert atmosphere; Stage #2: (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester In tetrahydrofuran; hexane at 20℃; for 12h; Inert atmosphere;	87%

2,6-dichloroquinoxaline (18671-97-1) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → (R)-(+)-methyl-2-[4-(6-chloro-2-quinoxalinyloxy)-phenoxy]-propionate (76578-71-7)

Conditions	Yield
With potassium carbonate In acetonitrile Heating;	85.2%

(2-aminomethylpyridine) (3731-51-9) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-(4-hydroxy-phenoxy)-N-pyridin-2-ylmethyl-propionamide

Conditions	Yield
for 7.5h; Heating;	85%

Cyclopropylamine (765-30-0) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → N-cyclopropyl-2-(4-hydroxy-phenoxy)-propionamide

Conditions	Yield
for 8h; Heating;	84%

2,3-dichlorophenol (576-24-9) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → methyl (S)-2-(2,3-dichlorophenoxy)propionate (1434518-91-8)

Conditions	Yield
Stage #1: 2,3-dichlorophenol; (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester With triphenylphosphine In dichloromethane at 0℃; for 0.166667h; Mitsunobu Displacement; Inert atmosphere; Stage #2: With diethylazodicarboxylate In dichloromethane at 20℃; for 24h; Mitsunobu Displacement;	83%
Stage #1: 2,3-dichlorophenol; (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester With triphenylphosphine In dichloromethane at 0℃; for 0.166667h; Inert atmosphere; Stage #2: With diethylazodicarboxylate In dichloromethane at 20℃; for 12h; Inert atmosphere;

4-(aminomethyl)pyridine (3731-53-1) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-(4-hydroxy-phenoxy)-N-pyridin-4-ylmethyl-propionamide

Conditions	Yield
for 3.5h; Heating;	81%

cyclopropanemethylamine (2516-47-4) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → N-cyclopropylmethyl-2-(4-hydroxy-phenoxy)-propionamide

Conditions	Yield
for 10h; Heating;	78%

3-Aminomethylpyridine (3731-52-0) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-(4-hydroxy-phenoxy)-N-pyridin-3-ylmethyl-propionamide

Conditions	Yield
for 5.5h; Heating;	72%

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-N-pyridin-3-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85.2 percent / K2CO3 / acetonitrile / Heating 2: 97 percent / 10 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-N-cyclopropylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85.2 percent / K2CO3 / acetonitrile / Heating 2: 87 percent / 3 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-N-pyridin-4-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85.2 percent / K2CO3 / acetonitrile / Heating 2: 76 percent / 7 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-N-pyridin-2-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85.2 percent / K2CO3 / acetonitrile / Heating 2: 80 percent / 14 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → N-benzo[1,3]dioxol-5-ylmethyl-2-[4-(6-chloro-quinoxalin-2-yloxy)-phenoxy]-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85.2 percent / K2CO3 / acetonitrile / Heating 2: 83 percent / 14 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-N-cyclopropyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 84 percent / 8 h / Heating 2: 68 percent / potassium carbonate / acetonitrile / 2 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-N-cyclopropylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 78 percent / 10 h / Heating 2: 88 percent / potassium carbonate / acetonitrile / 1.5 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-N-pyridin-4-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 81 percent / 3.5 h / Heating 2: 65 percent / potassium carbonate / acetonitrile / 3 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-N-pyridin-3-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 72 percent / 5.5 h / Heating 2: 62 percent / potassium carbonate / acetonitrile / 9 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → 2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-N-pyridin-2-ylmethyl-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 85 percent / 7.5 h / Heating 2: 88 percent / potassium carbonate / acetonitrile / 4 h / Heating View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → N-benzo[1,3]dioxol-5-ylmethyl-2-[4-(6-chloro-benzooxazol-2-yloxy)-phenoxy]-propionamide

Conditions	Yield
Multi-step reaction with 2 steps 1: 87 percent / 4.5 h / Heating 2: 67 percent / potassium carbonate / acetonitrile / 10 h / Heating View Scheme

methyl chloroacetate (96-34-4) + (R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → C13H16O6 (1412737-21-3)

Conditions	Yield
With disodium hydrogen phosphate; potassium carbonate; sodium iodide In acetone for 10h; Reflux;

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → [Cu(L)(bipy)(H2O)]

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium carbonate; sodium iodide; disodium hydrogen phosphate / acetone / 10 h / Reflux 2: hydrogenchloride / ethanol; water / 5 - 6 h / 60 °C 3: N,N-dimethyl-formamide; water / 48 h / 90 °C / Autoclave View Scheme

(R)-(+)-2-(4-hydroxyphenoxy)propionic acid methyl ester (96562-58-2) → Cu2(L)2(phen)4(H2O)13

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium carbonate; sodium iodide; disodium hydrogen phosphate / acetone / 10 h / Reflux 2: hydrogenchloride / ethanol; water / 5 - 6 h / 60 °C 3: water; methanol / 1 h / Autoclave View Scheme

Upstream product

• 67-56-1 methanol 
• 94050-90-5 (R)-2-(4-hydroxyphenoxy)propionic acid 
• 20047-41-0 methyl (2S)-2-bromopropanoate 
• 123-31-9 hydroquinone 
• 73246-45-4 methyl-(S)-2-chloropropionate 
• 60075-04-9 (RS)-methyl 2-(4-hydroxyphenoxy)propionate 
• 111842-06-9 methyl (R)-2-(4-acetoxyphenoxy)propionate 

Downstream Products

• 1412737-21-3 C₁₃H₁₆O₆ 
• 94050-90-5 (R)-2-(4-hydroxyphenoxy)propionic acid 
• 95721-12-3 (2R)-2-{4-[(6-chloro-1,3-benzothiazol-2-yl)oxy]phenoxy}propanoic acid 
• 1434518-91-8 methyl (S)-2-(2,3-dichlorophenoxy)propionate 
• 76578-71-7 (R)-(+)-methyl-2-[4-(6-chloro-2-quinoxalinyloxy)-phenoxy]-propionate 

Relevant articles and documents

Method for preparing (R)-(+)-2-(4-hydroxyphenoxy) methyl propionate

The invention provides a method for preparing (R)-(+)-2-(4-hydroxyphenoxy) methyl propionate, and belongs to the technical field of preparation of pesticide intermediates. The method for preparing (R)-(+)-2-(4-hydroxyphenoxy) methyl propionate comprises the following steps: mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R)-(+)-2-(4-hydroxyphenoxy) methyl propionate, wherein the halogenated methyl propionate is (S)-(-)-methyl-2-chloropropionate), (S)-(-)-methyl-2-bromopropionate or (S)-(-)-methyl-2-iodopropionate. According to the method, hydroquinone and halogenated methyl propionate are taken as raw materials, (R)-(+)-2-(4-hydroxyphenoxy) methyl propionate (MAQ) is synthesized in a polar aprotic solvent system through a one-step method, the process is simple, environment friendliness is achieved, the product quality is good, and the yield is high.

Preparation method of R-(+)-2-[4-(hydroxyphenoxy) propionate

The invention discloses a preparation method of a herbicide intermediate R-(+)-2-[4-(hydroxyphenoxy) propionate by using a novel solid acid catalyst. The method improves the traditional esterification process, reduces the discharge of wastewater, and plays great improvement role in preventing the inversion of configuration of a chiral product.

Preparation of mixtures of (R)- and (S)-2-(4-alkanoylphenoxy)- or (R)- and (S)-2-(4-aroylphenoxy)propionic esters

A mixture of (R)- and (S)-2-(4-alkanoylphenoxy)- or (R)- and (S)-2-(4-aroylphenoxy)propionic esters I STR1 with an enantiomeric excess of at least 90% is prepared by reacting a mixture of (R) and (S) enantiomer of a 2-phenoxypropionic ester II STR2 in which the appropriate (R) or (S) isomer is present in excess, with a carboxylic acid derivative of the formula III (X=OH, halogen, R1 COO or sulfonyloxy) in the presence of a Friedel-Crafts catalyst. The (R)- or (S)-2-(4-alkanoylphenoxy)propionic esters and (R)- or (S)-2-(4-hydroxyphenoxy)propionic esters are used for preparing crop protection agents and drugs.