(S)-(+)-3-Chloro-1,2-propanediol
[CAS 60827-45-4]

Identification

• Classification: Organic raw materials >> Alcohols, phenols, phenolic compounds and derivatives
• Name: (S)-(+)-3-Chloro-1,2-propanediol
• Synonyms: (S)-(+)-Glycerol alpha-monochlorohydrin
• Molecular Formula: C₃H₇ClO₂
• Molecular Weight: 110.54
• CAS Registry Number: 60827-45-4
• EC Number: 612-041-7
• SMILES: C([C@@H](CCl)O)O

Properties

• Density: 1.3$+/-$0.1 g/cm³ Calc.^*, 1.322 g/mL (Expl.)
• Boiling point: 213.0 $degree$C 760 mmHg (Calc.)^*, 213 $degree$C (Expl.)
• Flash point: 113.3$+/-$21.8 $degree$C (Calc.)^*, 126 $degree$C (Expl.)
• Index of refraction: 1.474 (Calc.)^*, 1.48 (Expl.)

^* Calculated using Advanced Chemistry Development (ACD/Labs) Software.

Safety Data

• Hazard Symbols: GHS05;GHS06;GHS07;GHS08 Danger
• Risk Statements: H301-H312-H315-H318-H330-H360
• Safety Statements: P203-P260-P264-P264+P265-P270-P271-P280-P284-P301+P316-P302+P352-P304+P340-P305+P354+P338-P316-P317-P318-P320-P321-P330-P332+P317-P362+P364-P403+P233-P405-P501

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Serious eye damage	Eye Dam.	1	H318
Acute toxicity	Acute Tox.	3	H301
Acute toxicity	Acute Tox.	4	H312
Skin irritation	Skin Irrit.	2	H315
Acute toxicity	Acute Tox.	2	H330
Acute toxicity	Acute Tox.	3	H311
Reproductive toxicity	Repr.	2	H361
Substances or mixtures corrosive to metals	Met. Corr.	1	H290
Acute toxicity	Acute Tox.	4	H332
Reproductive toxicity	Repr.	1A	H360
Specific target organ toxicity - repeated exposure	STOT RE	1	H372
Specific target organ toxicity - single exposure	STOT SE	1	H370
Acute toxicity	Acute Tox.	2	H300
Carcinogenicity	Carc.	2	H351

• Transport Information: UN 2689

Discovery and Applications

(S)-(+)-3-Chloro-1,2-propanediol is a chiral halohydrin, meaning it contains both a halogen substituent (chlorine) and a vicinal diol (two adjacent hydroxyl groups) on a three-carbon propane backbone. The “(S)-(+)” designation indicates that it is a specific enantiomer with defined absolute configuration and positive optical rotation.

Structurally, the molecule consists of a propane chain substituted with hydroxyl groups at positions 1 and 2, and a chlorine atom at position 3. The presence of the two hydroxyl groups makes it a diol, while the chlorine introduces a good leaving group, giving the molecule both nucleophilic and electrophilic reactivity within the same framework.

The chiral center is located at carbon 2, which is bonded to four different substituents: a hydroxymethyl group, a chloromethyl group, a hydrogen atom, and a hydroxyl-bearing carbon chain. This stereocenter is responsible for the enantiomeric properties of the compound, and different enantiomers can exhibit distinct biological or chemical behavior.

Halohydrins such as 3-chloro-1,2-propanediol are well known for their high reactivity in intramolecular substitution reactions. Under basic conditions, the hydroxyl group at C-2 can be deprotonated to form an alkoxide, which can then attack the carbon bearing the chlorine atom. This intramolecular SN2 reaction leads to the formation of epoxides, specifically epichlorohydrin-type structures. This reactivity makes halohydrins important intermediates in organic synthesis.

The vicinal diol structure contributes significantly to the compound’s polarity and hydrogen-bonding ability. Both hydroxyl groups can act as hydrogen bond donors and acceptors, increasing water solubility and enabling strong interactions with polar solvents. The presence of the chlorine atom adds polarizability and increases molecular reactivity toward nucleophilic substitution.

From a chemical standpoint, the compound is multifunctional: the hydroxyl groups can undergo oxidation, esterification, or ether formation, while the chlorine substituent can be replaced by nucleophiles such as amines, thiols, or alkoxides. This dual reactivity makes halohydrins valuable intermediates in the synthesis of epoxides, glycerol derivatives, and more complex chiral molecules.

The stereochemistry of (S)-(+)-3-chloro-1,2-propanediol is particularly important in synthetic and biological contexts. Enantiopure halohydrins are often used in asymmetric synthesis or as intermediates in the preparation of optically active epoxides. The configuration determines the stereochemical outcome of downstream reactions, especially intramolecular cyclization to epoxides, which proceeds with inversion of configuration at the reacting carbon.

In terms of physicochemical properties, this compound is expected to be highly polar and miscible with water or other polar solvents due to its diol functionality. The chlorine substituent slightly reduces polarity relative to a triol but increases reactivity. Hydrogen bonding plays a dominant role in its physical behavior, including boiling point and viscosity.

Halohydrins are also relevant in industrial chemistry. Compounds structurally related to 3-chloro-1,2-propanediol are used in the production of epichlorohydrin, which is a key intermediate in epoxy resin manufacturing. Epoxides derived from halohydrins are widely used in polymers, adhesives, and coatings.

Overall, (S)-(+)-3-chloro-1,2-propanediol is a chiral halohydrin characterized by a combination of hydroxyl and chloro functional groups on a three-carbon backbone. Its significance lies in its high chemical reactivity, stereochemical importance, and role as a precursor to epoxides and other valuable synthetic intermediates.

References

2024. Structural insights into the distinct substrate preferences of two bacterial epoxide hydrolases. International Journal of Biological Macromolecules.
DOI: 10.1016/j.ijbiomac.2024.130419

2023. Toxicology of 3-monochloropropane-1,2-diol and its esters: a narrative review. Archives of Toxicology.
DOI: 10.1007/s00204-023-03467-7