96-24-2

Usage

Uses

Used in Organic Synthesis:
3-Chloro-1,2-propanediol is used as an intermediate for the synthesis of glycerol esters, amines, and other derivatives. It is also used as a solvent for preparing a plasticizer, a surfactant, a dye intermediate, a drug, or as a dye intermediate mainly for use as an acetyl fiber or the like.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 3-Chloro-1,2-propanediol is used in the production of phlegm and phlegm-removing guaiac oil ether, antiasthmatic drug theophylline, and hydroxyphylline.
Used in Food Industry:
3-Chloro-1,2-propanediol may be used as a reference standard for the determination of 3-chloro-1,2-propanediol in food samples by gas chromatography with mass spectrometric detection (GC-MS).
Used in Explosives Industry:
It is used to lower the freezing point of dynamite.
Used as a Rodent Chemosterilant:
3-Chloro-1,2-propanediol is used as a rodent chemosterilant.
Used in the Manufacture of Dye Intermediates:
3-Chloro-1,2-propanediol is used in the manufacture of dye intermediates.

Sources

https://en.wikipedia.org/wiki/3-MCPD https://www.sigmaaldrich.com/catalog/product/aldrich/107271?lang=en®ion=US Gunn, S. A., T. C. Gould, and W. A. Anderson. "Possible mechanism of posttesticular antifertility action of 3-chloro-1, 2-propanediol. " Proceedings of the Society for Experimental Biology & Medicine Society for Experimental Biology & Medicine 132.2(1969): 656.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 1, p. 294, 1941Synthetic Communications, 24, p. 1959, 1994 DOI: 10.1080/00397919408010203Synthesis, p. 295, 1989

Reactivity Profile

3-Chloro-1,2-propanediol is hygroscopic and may be sensitive to prolonged exposure to air. Glycols and their ethers undergo violent decomposition in contact with approximately 70% perchloric acid. .

Health Hazard

Glycerol α-monochlorohydrin is a highlytoxic, teratogenic, and carcinogenic com pound. It is also an eye irritant.Inhalation of 125 ppm in 4 hours wasfatal to rats. The lethal dose on mice viaintraperitoneal route was 10 mg/kg. Lowdosage can cause sleepiness, and on chronicexposure, weight lossLD50 value, oral (rats): 26 mg/k3-Chloro-1,2-propanediol is a strong teratomer,causing severe reproductive effects. Animal studies indicated that the adverse effects wereof spermatogenesis type, related to the testes,sperm duct, and Cowper’s gland. These werepaternal effectsStudies on rats indicated that high exposure levels to glycerol chlorohydrin can giverise to thyroid tumors.

Health Hazard

TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

Fire Hazard

Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

Flammability and Explosibility

Nonflammable

Safety Profile

Poison by ingestion and intraperitoneal routes. Moderately toxic by inhalation. Experimental reproductive effects. A severe eye irritant. Questionable carcinogen with experimental tumorigenic data. Mutation data reported. A chemosterilant for rodents. Combustible when exposed to heat or flame. Reaction with perchloric acid forms a sensitive explosive product more powerful than glyceryl nitrate. When heated to decomposition it emits toxic fumes of Cl-.

Waste Disposal

Chemical incineration is the most appropriatemethod of disposal.

InChI:InChI=1/C3H7ClO2/c4-2-1-3(5)6/h3,5-6H,1-2H2

Upstream product

• 51483-40-0 1,3-dibromo-2-chloro-propane 
• 563-63-3 silver(I) acetate 
• 556-52-5 oxiranyl-methanol 
• 107-18-6 allyl alcohol 
• 56-81-5 glycerol 
• 107-05-1 3-chloroprop-1-ene 
• 106-89-8 epichlorohydrin 
• 110-65-6 1,4-dihydroxybut-2-yne 
• 321997-45-9 hypophosphorous acid 2-hydroxypropyl ester 
• 5503-32-2 2-1,4-dioxaspiro<4,5>decane 
• 66089-98-3 methyl-2 phenyl-2 chloromethyl-4 dioxolanne-1,3 
• 71-41-0 pentan-1-ol 
• 127-65-1 chloroamine-T 
• 75-56-9 methyloxirane 

Downstream Products

• 4847-93-2 3-piperidin-1-yl-propane-1,2-diol 
• 58403-04-6 4-chloromethyl-2-furan-2-yl-[1,3]dioxolane 
• 13729-88-9 1-(2,3-dihydroxy-propyl)-quinolinium; chloride 
• 5579-92-0 1-(2,3-dihydroxy-propyl)-3,5-diiodo-1H-pyridin-4-one 
• 479-18-5 diprophylline 
• 13460-96-3 1-(2,3-dihydroxy-propyl)-3,7-dimethyl-3,7-dihydro-purine-2,6-dione 
• 109812-05-7 3-(2,3-dihydroxy-propyl)-2-phenyl-3H-quinazolin-4-one 
• 111038-24-5 7-(2,3-Dihydroxypropyl)-8-bromotheophylline 
• 869-50-1 1,2-diacetoxy-3-chloro-propane 
• 64049-48-5 2-(2,3-dihydroxy-propoxy)-benzaldehyde 
• 99360-02-8 phenyl-carbamic acid-(3-chloro-2-hydroxy-propyl ester) 
• 56266-47-8 1,2-bis-(2,3-dihydroxy-propoxy)-benzene 
• 145094-05-9 phosphoric acid-(β,β'-dihydroxy-isopropyl ester)-(2,3-dihydroxy-propyl ester) 
• 5149-48-4 3-(phenylthio)-1,2-propanediol 

Relevant academic research and scientific papers

Thermokinetics of reactions with liquid-liquid phase separation

Isothermal heat flow calorimetry with controlled thermoelectric cooling resp. heating is applied to study the critical slowing down of the kinetics of reactions with liquid-liquid phase separation. Results (i) on the acid-catalysed hydrolysis of chloromethyloxirane by water, and (ii) on the ring-opening and esterification of bromomethyloxirane by dichloroacetic acid in the presence of cyclohexane as an inert solvent, both at 298.15 K, are presented. The heat production w(t) which is proportional to the reaction rate ?ζ/?t (where ζ, is the reaction coordinate) exhibits a funnel-like fall-off when the reaction path intersects the binodal curve at the critical solution point CP. From the shape of this part of the w(t) curves an average value of the critical exponent Φ = 0.72±0,003, which refers to the change of ζ with t at constant T and p, is calculated. This result is to be compared with the theoretical value of Φ = 0.708 obtained from a modification of the Griffiths and Wheeler theory of critical points in multicomponent systems to chemically reacting systems far from equilibrium by introducing f as an additional extensive variable. This allows the critical slowing down of the reaction rates to be interpreted as resulting from the divergence of the correlation length ζ, resp. from the convergence of the transport phenomena to zero at the CP. ? VCH Verlagsgesellschaft mbH, 1996.

Curing Behavior and Properties of Sustainable Furan-Based Epoxy/Anhydride Resins

The last two decades have witnessed a significant growth in using bioderived materials, driven by the necessity of replacing fossil-derived precursors, reducing the fossil fuel consumption, and lowering the global environmental impact. This is possible thanks to the availability of abundant resources from biomasses and the development of optimized technologies based on the principles of sustainability and circular economy. Herein, we report on the synthesis and characterization of new carbohydrate-derived epoxy resins. In particular, 2,5-bis[(oxiran-2-ylmethoxy)methyl]furan has been synthesized and cured with methyl nadic anhydride. The effect of different initiators was studied, in order to identify the most efficient curable formulations. A series of resins was then prepared varying the epoxide-anhydride ratios. The results gathered from physicochemical, mechanical, morphological analyses have demonstrated that the produced furan-based thermosets have the potential to be proposed as sustainable alternatives to the traditional, bisphenol A-containing epoxy resins.

Method for producing 3-chloro-1,2-propylene glycol by using acetic anhydride-modified graphene oxide

The invention relates to a method for producing 3-chloro-1,2-propylene glycol by using an acetic anhydride-modified graphene oxide catalyst. The method comprises the following steps: using solid acetic anhydride-modified graphene oxide (AGO) as a catalyst, adding hydrochloric acid and glycerol into a reaction kettle, performing heating to 50-110 DEG C in a nitrogen atmosphere, performing stirringreaction for 2-10 hours, performing cooling to 30-60 DEG C, centrifugally separating the catalyst and a reaction solution, and rectifying the reaction liquid under reduced pressure to obtain a product3-chloro-1,2-propylene glycol shown in a formula (I). The method is simple in process, and the catalyst can be recycled. The conversion rate of the reactant glycerol can reach 95% or above, and the selectivity of the product 3-chloro-1,2-propylene glycol can reach 80% or above.

Sterically controlling 2-carboxylated imidazolium salts for one-step efficient hydration of epoxides into 1,2-diols

In order to overcome the disadvantages of excessive water and many byproducts in the conventional process of epoxide hydration into 1,2-diols, 2-carboxylated imidazolium salts were first adopted as efficient catalysts for one-step hydration of epoxides into 1,2-diols. By regulating the cation chain lengths, different steric structures of 2-carboxylated imidazolium salts with chain lengths from C1 to C4 were prepared. The salt with the shortest substituent chain (DMIC) exhibited better thermal stability and catalytic performance for hydration, achieving nearly 100% ethylene oxide (EO) conversion and 100% ethylene glycol (EG) selectivity at 120 °C, 0.5 h with just 5 times molar ratio of H2O to EO. Such a tendency is further confirmed and explained by both XPS analysis and DFT calculations. Compared with other salts with longer chains, DMIC has stronger interaction of CO2?anions and imidazolium cations, exhibiting a lower tendency to release CO2?and form HO-CO2?, which can nucleophilically attack and synergistically activate ring-opening of epoxides with imidazolium cations. The strong huge sterically dynamic structure ring-opening transition state slows down the side reaction, and both cations and anions stabilized the transition state imidazolium-EG-HO-CO2?, both of which could avoid excessive hydration into byproducts, explaining the high 1,2-diol yield. Based on this, the cation-anion synergistic mechanism is then proposed.

Hydrogen-Catalyzed Acid Transformation for the Hydration of Alkenes and Epoxy Alkanes over Co-N Frustrated Lewis Pair Surfaces

Hydrogen (H2) is widely used as a reductant for many hydrogenation reactions; however, it has not been recognized as a catalyst for the acid transformation of active sites on solid surface. Here, we report the H2-promoted hydration of alkenes (such as styrenes and cyclic alkenes) and epoxy alkanes over single-atom Co-dispersed nitrogen-doped carbon (Co-NC) via a transformation mechanism of acid-base sites. Specifically, the specific catalytic activity and selectivity of Co-NC are superior to those of classical solid acids (acidic zeolites and resins) per micromole of acid, whereas the hydration catalysis does not take place under a nitrogen atmosphere. Detailed investigations indicate that H2 can be heterolyzed on the Co-N bond to form Hδ-Co-N-Hδ+ and then be converted into OHδ-Co-N-Hδ+ accompanied by H2 generation via a H2O-mediated path, which significantly reduces the activation energy for hydration reactions. This work not only provides a novel catalytic method for hydration reactions but also removes the conceptual barriers between hydrogenation and acid catalysis.

In situconstruction of phenanthroline-based cationic radical porous hybrid polymers for metal-free heterogeneous catalysis

Rational design of multifunctional radical porous polymers with redox activity for targeted metal-free heterogeneous catalysis is an important research topic. In this work, we reported a new class of phenanthroline-based cationic radical porous hybrid polymers (Phen˙+-PHPs), which were constructed from the Heck reaction between a newly designed dibromo-substituted phenanthroline ionic monomer (iDBPhen) and a rigid building block, octavinylsilsesquioxane (VPOSS). For the first time, the stable phenanthroline-based radical cation was unexpectedly discovered in these polyhedral oligomeric silsesquioxane (POSS)-based porous hybrid polymers, probably undergoingin situreduction of the dicationic monomer iDBPhen during the alkaline reagent K2CO3-involved Heck reaction. The radical characters of the typical porous polymers Phen˙+-PHP-2 and Phen˙+-PHP-2Br were confirmed from the electron paramagnetic resonance (EPR) spectra and X-ray photoelectron spectra (XPS). The chemical structures and porous geometry were fully characterized by a series of advanced technologies. Surprisingly, the metal-free cationic radical polymer Phen˙+-PHP-2 exhibited high heterogeneous catalytic efficiency in the H2O2-mediated selective oxidation of various sulfides to sulfoxides with high yields under mild conditions, owing to the electron-accepting and redox ability of Phen-based dications and radical cations. Moreover, the extended sample Phen˙+-PHP-2Br prepared by post-treatment of Phen˙+-PHP-2 with aqueous HBr was also employed as a metal-free efficient heterogeneous catalyst in the conversion of CO2with epoxides into cyclic carbonates under atmospheric pressure and low temperatures. The remarkable catalytic performance in CO2conversion should be assigned to the synergistic catalysis of POSS-derived Si-OH groups and nucleophilic Br?anions and N active atom-involved Phen cationic radical moieties within Phen˙+-PHP-2Br. These two catalysts can be facilely recovered and reused, also with stable recyclability in the above catalytic reaction systems, achieving the heterogeneous catalytic demands for multipurpose reactions.

Selective synthesis of epichlorohydrin: Via liquid-phase allyl chloride epoxidation over a modified Ti-MWW zeolite in a continuous slurry bed reactor

The epoxidation of allyl chloride (ALC) to epichlorohydrin (ECH) with H2O2 using a piperidine (PI)-modified Ti-MWW catalyst (Ti-MWW-PI) in a continuous slurry reactor was investigated to develop an efficient reaction system for the corresponding industrial process. The reaction parameters, including solvent, reaction temperature, t-butanol/ALC mass ratio, ALC/H2O2 molar ratio, weight hourly space velocity of H2O2, and the addition amount of ammonia, were studied in detail to pursue high H2O2 conversion and ECH selectivity. A long catalytic lifetime of 244 h was achieved at high H2O2 conversion (>97.0%) and ECH selectivity (>99.8%) under optimized reaction conditions. The crystallinity was well maintained for the deactivated Ti-MWW-PI catalyst, which was regenerated by a combination of calcination and piperidine treatment. This journal is

Novel method for producing 2-amino-1, 3-propylene glycol by JIT method

The invention belongs to the field of fine chemical engineering, and relates to a novel method for producing 2-amino-1, 3-propylene glycol by a JIT method, the novel method is composed of a catalytic chlorination reaction and a catalytic amination reaction, glycerol is chlorinated by hydrogen chloride under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propylene glycol, and the 2-chloro-1, 3-propylene glycol is subjected to a catalytic reaction by urotropin to obtain 2-chloro-1, 3-propylene glycol.

Preparation method for 1,3-propylene glycol from glycerol

The invention relates to a preparation method for 1,3-propylene glycol from glycerol, wherein the preparation method comprises the steps of chlorohydrination reaction, cyclization reaction, hydrogenation reaction and the like. The glycerin conversion rate of the preparation method reaches 99% or above, the yield of 1,3-propylene glycol reaches 65% or above, and the preparation method has the advantages of being simple in process, mild in reaction condition, small in investment, high in technical safety and easy to operate and control.

Continuous flow upgrading of glycerol toward oxiranes and active pharmaceutical ingredients thereof

A robust continuous flow procedure for the transformation of bio-based glycerol into high value-added oxiranes (epichlorohydrin and glycidol) is presented. The flow procedure features a central hydrochlorination/dechlorination sequence and provides economically and environmentally favorable conditions involving an organocatalyst and aqueous solutions of hydrochloric acid and sodium hydroxide. Pimelic acid (10 mol%) shows an exceptional catalytic activity (>99% conversion of glycerol, a high selectivity toward 1,3-dichloro-2-propanol and 81% cumulated yield toward intermediate chlorohydrins) for the hydrochlorination of glycerol (140 °C) with 36 wt% aqueous HCl. These conditions are validated on a sample of crude bio-based glycerol. The dechlorination step is effective (quantitative conversion based on glycerol) with concentrated aqueous sodium hydroxide (20 °C) and can be directly concatenated to the hydrochlorination step, hence providing a ca. 2:3 separable mixture of glycidol and epichlorohydrin (74% cumulated yield). An in-line membrane separation unit is included downstream, providing usable streams of epichlorohydrin (in MTBE, with an optional concentrator) and glycidol (in water). The scalability of the dechlorination step is then assessed in a commercial pilot-scale continuous flow reactor. Next, bio-based epichlorohydrin is further utilized for the continuous flow preparation of β-amino alcohol active pharmaceutical ingredients including propranolol (hypertension, WHO essential), naftopidil (prostatic hyperplasia) and alprenolol (angina pectoris) within a concatenable two-step procedure using a FDA class 3 solvent (DMSO). This work provides the first example of direct upgrading of bio-based glycerol into high value-added pharmaceuticals under continuous flow conditions.