74497-15-7

Basic information

• Product Name: ETHYL (S)-2-CHLORO PROPIONATE
• Synonyms: (S)-2-Chloropropionic Ethyl Ester;(S)-2-Chloropropanoic acid ethyl ester;Ethyl L-alpha-chloropropionate;JEAVBVKAYUCPAQ-BYPYZUCNSA-N
• CAS NO: 74497-15-7
• Molecular Formula: C₅H₉ClO₂
• Molecular Weight: 136.58
• Product Categories: CHIRAL COMPOUNDS
• Mol File: 74497-15-7.mol
• Article Data: 4

Chemical Properties

• Boiling Point: 149℃
• Flash Point: 50℃
• Appearance: /
• Density: 1.081
• CAS DataBase Reference: ETHYL (S)-2-CHLORO PROPIONATE(CAS DataBase Reference)
• NIST Chemistry Reference: ETHYL (S)-2-CHLORO PROPIONATE(74497-15-7)
• EPA Substance Registry System: ETHYL (S)-2-CHLORO PROPIONATE(74497-15-7)

Safety Data

• Hazardous Substances Data: 74497-15-7(Hazardous Substances Data)

Usage

General Description

Ethyl (s)-2-chloro propionate is a chemical compound with the molecular formula C5H9ClO2. It is an ester of ethyl alcohol and (s)-2-chloro propionic acid. Ethyl (s)-2-chloro propionate is used as a reagent in organic chemistry reactions, particularly in the synthesis of various pharmaceuticals and agrochemicals. It is also utilized in the production of fragrances and flavors. Ethyl (s)-2-chloro propionate is a colorless, clear liquid with a strong, fruity odor. It is flammable and should be handled with care in a well-ventilated environment.

Synthetic route

(R)-Ethyl lactate (7699-00-5) → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide for 3.5h; Ambient temperature;	32%
With pyridine; thionyl chloride at 60℃;
With quinoline; thionyl chloride at 60℃;

ethyl 2-hydroxypropionate (97-64-3, 2676-33-7) → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
With pyridine; thionyl chloride

O-chlorosulfinyl-D-lactic acid ethyl ester (114983-33-4) → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
bei der Destillation;

(R)-Ethyl lactate (7699-00-5) + p-toluenesulfonyl chloride (98-59-9) → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
With pyridine

(S)-Ethyl lactate (687-47-8) → (+)-ethyl 2-chloropropionate (74497-15-7) + (R)-ethyl 2-chloropropanoate (42411-39-2)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide for 3h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With calcium fluoride; thionyl chloride In neat (no solvent) at 70 - 170℃; for 13h; Reagent/catalyst; Overall yield = 74 %;	A n/a B n/a
With calcium fluoride; thionyl chloride In neat (no solvent) at 70 - 170℃; for 17h; Overall yield = 60 %;	A n/a B n/a

thionyl chloride (7719-09-7) + (R)-Ethyl lactate (7699-00-5) → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
at 60℃; in Gegenwart von tertiaeren Basen;

pyridine (110-86-1) + (R)-Ethyl lactate (7699-00-5) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → (+)-ethyl 2-chloropropionate (74497-15-7)

quinoline (91-22-5) + (R)-Ethyl lactate (7699-00-5) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → (+)-ethyl 2-chloropropionate (74497-15-7)

(R)-Ethyl lactate (7699-00-5) + N,N-dimethyl-aniline (121-69-7) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → (+)-ethyl 2-chloropropionate (74497-15-7)

D(+)-chlorosulfinyllactic acid ethyl ester → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
unter Destillieren;
With pyridine; diethyl ether

D(+)-p-toluenesulfinyllactic acid ethyl ester → (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
With chlorine

pyridine hydrochloride (628-13-7) + d(+)-p-toluene-sulfonyl-lactic acid ethyl ester → (+)-ethyl 2-chloropropionate (74497-15-7)

D(+)-p-toluenesulfinyllactic acid ethyl ester → (S)-Ethyl lactate (687-47-8) + (+)-ethyl 2-chloropropionate (74497-15-7)

Conditions	Yield
With hypochloric acid

D-ethyl lactate → (+)-ethyl 2-chloropropionate (74497-15-7) + D-phosphoric acid bis-(1-ethoxycarbonyl-ethyl ester)

Conditions	Yield
With phosphorus trichloride at -10℃;

(R)-Ethyl lactate (7699-00-5) + PCl3 (0.33 mol) → (+)-ethyl 2-chloropropionate (74497-15-7) + D-phosphoric acid bis-(1-ethoxycarbonyl-ethyl ester)

Conditions	Yield
at -10℃;

pyridine (110-86-1) + (R)-Ethyl lactate (7699-00-5) + p-toluenesulfonyl chloride (98-59-9) → (+)-ethyl 2-chloropropionate (74497-15-7) + d(+)-p-toluenesulfonyl-lactic acid ethyl ester

Conditions	Yield
in der Waerme;
bei laengerer Einw.;

pyridine (110-86-1) + diethyl ether (60-29-7) + O-chlorosulfinyl-D-lactic acid ethyl ester (114983-33-4) → (+)-ethyl 2-chloropropionate (74497-15-7) + N-<1-ethoxycarbonyl-ethyl>-pyridinium picrate

Conditions	Yield
Behandeln das entstehende Produkt mit Pikrinsaeure in verduenntem Aethanol;

(R)-Ethyl lactate (7699-00-5) → (+)-ethyl 2-chloropropionate (74497-15-7) + (R)-ethyl 2-chloropropanoate (42411-39-2)

Conditions	Yield
With pyridine; thionyl chloride at 20℃; Inert atmosphere; enantioselective reaction;	A n/a B n/a

(+)-ethyl 2-chloropropionate (74497-15-7) + 6-chloro-2-(4-hydroxyphenoxy)quinoxaline (76578-79-5) → (R)-2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]propanoic acid ethyl ester (76578-14-8)

Conditions	Yield
With tetrabutylammomium bromide; triethylamine In toluene at 60℃; for 4h; Solvent; Temperature; Reflux;	95.1%

(+)-ethyl 2-chloropropionate (74497-15-7) → (S)-2-chloropropanoic acid (29617-66-1)

Conditions	Yield
With sodium hydroxide In water	85%

(+)-ethyl 2-chloropropionate (74497-15-7) + benzylamine (100-46-9) → (S)-(-)-N-Benzyl-2-chloropropionamide (119817-95-7)

Conditions	Yield
With aluminium trichloride for 22h;	70%

2,6-Dichlorophenol (87-65-0) + (+)-ethyl 2-chloropropionate (74497-15-7) → (-)-ethyl 2-(2,6-dichlorophenoxy)propionate (383898-16-6)

Conditions	Yield
With potassium methanolate 1.) 2-butanone, 40 deg C, 1 h, 2.) 2-butanone, reflux, 48 h; Yield given. Multistep reaction;

rac-octan-2-ol (4128-31-8) + (+)-ethyl 2-chloropropionate (74497-15-7) → (S)-2-Octanol (6169-06-8) + (R)-1-Methylheptyl (L)-2-chloropropanoate (129974-86-3)

Conditions	Yield
lipase CC In hexane Product distribution; lipase P;
lipase CC In hexane lipase P;
lipase CC In hexane Product distribution;
With CC lipase In hexane at 40℃;

(+)-ethyl 2-chloropropionate (74497-15-7) + menthol (89-78-1) → (3S)-3-methyl-6-(1-methylethyl)cyclohexanol (89-78-1, 490-99-3, 491-01-0, 491-02-1, 1490-04-6, 2216-51-5, 2216-52-6, 3623-51-6, 3623-52-7, 3623-53-8, 15356-60-2, 15356-70-4, 20747-49-3, 20752-33-4, 20752-34-5, 23283-97-8, 64282-88-8) + (1R)-Menthyl (L)-2-chloropropanoate (55284-69-0, 130060-51-4, 130060-52-5, 130060-53-6)

Conditions	Yield
lipase CC In hexane Product distribution;
lipase CC In hexane Product distribution; lipase P;
lipase CC In hexane or lipase P;

(S)-1-(1-phenylpropyl)-biguanide + (+)-ethyl 2-chloropropionate (74497-15-7)

→ ethyl (R)-2-(4-methoxyphenoxy)propanoate (640997-22-4)

Conditions	Yield
With sodium hydroxide In water	n/a

(+)-ethyl 2-chloropropionate (74497-15-7) + 4-hydroxy-benzaldehyde (123-08-0) → C12H14O4

Conditions	Yield
With sodium hydroxide In water	n/a

(+)-ethyl 2-chloropropionate (74497-15-7) + hydroquinone (123-31-9) → (R)-2-(4-hydroxyphenoxy)propionic acid ethyl ester (71301-98-9)

Conditions	Yield
With sodium hydroxide In water Product distribution / selectivity;	n/a

Upstream product

• 97-64-3 ethyl 2-hydroxypropionate 
• 114983-33-4 O-chlorosulfinyl-D-lactic acid ethyl ester 
• 687-47-8 (S)-Ethyl lactate 
• 110-86-1 pyridine 
• 7699-00-5 (R)-Ethyl lactate 
• 98-59-9 p-toluenesulfonyl chloride 
• 60-29-7 diethyl ether 
• 687-47-8 (-)-ethyl lactate 
• 760-11-2 (-)-Chlorsulfonsaeure-(1-aethoxycarbonyl-aethylester) 
• 628-13-7 pyridine hydrochloride 
• 121-69-7 N,N-dimethyl-aniline 
• 10025-87-3 trichlorophosphate 
• 91-22-5 quinoline 
• 7719-09-7 thionyl chloride 

Downstream Products

• 383898-16-6 (-)-ethyl 2-(2,6-dichlorophenoxy)propionate 
• 119817-95-7 (S)-(-)-N-Benzyl-2-chloropropionamide 
• 640997-22-4 ethyl (R)-2-(4-methoxyphenoxy)propanoate 
• 29617-66-1 (S)-2-chloropropanoic acid 
• 76578-14-8 (R)-2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]propanoic acid ethyl ester 
• 71301-98-9 (R)-2-(4-hydroxyphenoxy)propionic acid ethyl ester 
• 89-78-1 (3S)-3-methyl-6-(1-methylethyl)cyclohexanol 
• 55284-69-0 (1R)-Menthyl (L)-2-chloropropanoate 
• 6169-06-8 (S)-2-Octanol 
• 129974-86-3 (R)-1-Methylheptyl (L)-2-chloropropanoate 

Relevant articles and documents

Optimization of the use of a chiral bio-based building block for the manufacture of DHPPA, a key intermediate for propionate herbicides

An alternative route for the production of (R)-2-(4-hydroxyphenoxy) propionic acid (DHPPA), a key intermediate in herbicide chemistry, is proposed. This route makes use of a chiral building block, initially produced by fermentation. The route has been optimized based on two steps: chlorination and etherification. The chlorination step has a maximum ee of 99% and a yield of 85% after distillation. The etherification step has a yield of 66%. Comparison of the route with the industrial standard shows a significant improvement in terms of green chemistry: waste streams are lowered up to 7-fold and the toxicity of the waste streams is reduced. This journal is the Partner Organisations 2014.

Synthesis of enantiomerically pure (R)- and (S)-2-sulfanylpropanoic acids ('thiolactic acid') from ethyl (S)-lactate using pig liver esterase

The methanesulfonates of optically pure ethyl (S)-lactate or ethyl (R)-2-chloropropanoate 5, obtained with inversion of configuration from ethyl (S)-lactate on treatment with SOCl2, can be substituted by caesium thiolates with inversion of configuration to yield (R) and (S) ethyl 2-(acetylsulfanyl)propanoate, 2a and 2b, respectively.Hydrolysis of the carboxy ester of 2a, 2b to the acid under common acidic or basic conditions always leads to substantial racemisation.However, the use of the mild biocatalyst pig liver esterase (PLE) at neutral pH yields the carboxylic acids 4a and 4b without racemisation.The acetylsulfanyl group remains unaffected during this process.Subsequent treatment of the acetylsulfanyl group of 4a or 4b with 2 mol dm-3 aqueous ammonia leads to the useful optically pure building block (R)- or (S)-2-sulfanylpropanoic acid ('thiolactic acid') 3a, 3b in an overall yield of 65percent based on cheap ethyl (S)-lactate.