598-38-9

Usage

Uses

Used in Chemical Synthesis:
2,2-Dichloroethanol is used as a reagent in the preparation of tunable molecular catalysts via functionalizing the methylene bridge of bis(N-heterocyclic carbene) ligands. This application takes advantage of its chemical properties to facilitate the synthesis of catalysts that can be tailored for specific chemical reactions.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 2,2-dichloroethanol is utilized as a solvent for the synthesis of various drugs and active pharmaceutical ingredients. Its ability to dissolve a wide range of compounds makes it a versatile and valuable component in the development of new medications.
Used in Industrial Chemical Production:
2,2-Dichloroethanol is also employed in the production of other industrial chemicals, such as ethylene glycol, which is used in the manufacturing of antifreeze, polyester fibers, and polyethylene terephthalate (PET) plastics. Its role in these processes highlights its importance in the broader chemical industry.
Used in Laboratory Research:
Due to its unique chemical properties, 2,2-dichloroethanol is often used in laboratory settings for research purposes. It serves as a valuable tool for chemists to study various chemical reactions and develop new synthetic methods, contributing to the advancement of chemical science.

Air & Water Reactions

Water soluble.

Reactivity Profile

2,2-DICHLOROETHANOL is incompatible with oxidizing agents.

Fire Hazard

2,2-DICHLOROETHANOL is combustible.

InChI:InChI=1/C2H4Cl2O/c3-2(4)1-5/h2,5H,1H2

Upstream product

• 79-43-6 dichloro-acetic acid 
• 79-36-7 dichloroacethyl chloride 
• 79-02-7 2,2-dichloroacetaldehyde 
• 535-15-9 ethyl 1,1-dichloroacetate 
• 110-91-8 morpholine 
• 127935-87-9 2,2-dichloroethyl nitrite 
• 75-89-8 2,2,2-trifluoroethanol 
• 94669-98-4 1-(4-methoxy-3-nitrophenyl)ethyl 2,2-dichloroethyl ether 
• 94670-09-4 {4-[1-(2,2-Dichloro-ethoxy)-ethyl]-phenyl}-dimethyl-amine; compound with perchloric acid 
• 94670-22-1 1-[1-(2,2-Dichloro-ethoxy)-ethyl]-4-methoxy-benzene 
• 108743-23-3 Acetaldehyd-mono-<2,2-dichlor-ethylacetal> 
• 67796-29-6 (2,2-dichloro-ethoxy)-methanol 
• 23273-87-2 C₂H₃Cl₂ 
• 64020-50-4 2-(2,2-dichloroethoxy)-2-phenyl-1,3-dioxolane 

Downstream Products

• 79-00-5 1,1,2-trichloroethane 
• 97631-93-1 2-chloro-benzoic acid-(2,2-dichloro-ethyl ester) 
• 97640-40-9 4-chloro-benzoic acid-(2,2-dichloro-ethyl ester) 
• 55505-16-3 (2,2-Dichloro-ethoxysulfonyl)-phenyl-acetic acid 
• 683-53-4 2-bromo-1,1-dichloro-ethane 
• 89123-83-1 Chlor-essigsaeure-<2.2-dichlor-aethylester> 
• 28049-04-9 3-phenylpropionic acid 2,2-dichloroethyl ester 
• 89691-63-4 1-(3-methoxy)-phenylethanol 
• 3319-15-1 rac-1-(4-methoxyphenyl)-ethanol 
• 94670-31-2 1-(4-methoxyphenyl)ethyl trifluoroethyl ether 
• 94670-22-1 1-[1-(2,2-Dichloro-ethoxy)-ethyl]-4-methoxy-benzene 
• 536-50-5 CH₃C₆H₄CH(CH₃)OH 

Relevant academic research and scientific papers

Predominant role of basicity of leaving group in α-effect for nucleophilic ester cleavage

It has been found that α-effects in nucleophilic reactions, unexpectedly large nucleophilicity due to adjacent unpaired electrons, are strongly dependent on the structure of substrate. The nucleophilic cleavages of 4-nitrobenzoate esters and 4-methylbenzo

The mechanism of the metal ion promoted cleavage of RNa phosphodiester bonds involves a general acid catalysis by the metal aquo ion on the departure of the leaving group

A series of uridine 3′-alkyl phosphates and 3′-aryl phosphates were synthesised and their cleavage was studied in the presence of Zn2+ aquo ions. A βlg value was determined for the Zn2+ promoted cleavage of both types of compounds. Comparison of the results obtained to those reported previously for the cleavage of the same substrates in the absence of metal ion catalysts suggests that the alkyl leaving group departs as an alcohol in the presence of metal ion catalysts. Furthermore, metal ion catalysts seem to enhance the departure. The aryl leaving group, in contrast, departs as an oxyanion.

Acylphosphonate hemiketals - Formation rate and equilibrium. The electron-withdrawing effect of dimethoxyphosphinyl group

Examination of alcoholic solutions of dimethyl acetylphosphonate (1) and dimethyl benzoylphosphonate (2) by 31P NMR spectroscopy reveals the presence of considerable amounts of hemiketals. Because of the great difference between the 31P chemical shifts of acylphosphonates (ca. 0 ppm) and their hemiketals (17-21 ppm), 31P NMR spectroscopy is a uniquely suitable method for studying the rates and equilibria of hemiketal formation of acylphosphonates with different alcohols. The equilibrium constants Kf, K′f (K′f = Kf[ROH]), pseudo-first-order rate constants k′f, the second order rate constants, kf for hemiketal formation from dimethyl acetylphosphonate with various alcohols, as well as the reverse reaction rate constants, kr to starting materials, were determined. The kinetic isotope effect of 2.8 for the forward reaction kf (EtOH addition) and the backward reaction kr indicates a general catalysis pathway. On the other hand, the calculated values of the enthalpies of activation ΔH? = 10.37 kcal mol-1 (forward), ΔH? = 13.66 kcal mol-1 (backward) and the entropies of activation, ΔS? = -17.25 cal mol-1 K-1 (forward), ΔS? = -9.82 cal mol-1 K-1 (backward) are not in accord with high molecularity of the reaction (1 cal = 4.184 J). Our analysis led to the conclusion that this is probably due to the fact that the transition state is mainly reactant-like with the development of only limited extent of bond formation. Various plausible reaction pathways for hemiketal formation are discussed. In addition, we have calculated the value of 2.65 σ* for the P(O)(OMe)2 group based on proton affinity obtained from heats of formation (ΔHf) of applying the MNDO techniques. The following linear correlation between pKa values and PA values of hemiketals of the form (Me)(R)C(OH)(OCH2X) was developed: pKa = PA - 356.58 + 9.18 [σ*(Me) + σ*(R) + 0.2σ*(X)].

Intramolecular Nucleophilic Reactions of Dialkyl 1,1-Dichloro-2-hydroxyethylphosphonates

Methods are developed for preparing dialkyl (1,1-dichloro-2-hydroxyethyl)phosphonates. Under the action of sodium hydride these esters enter into intramolecular nucleophilic reactions via two routes yielding α-ketophosphonates and phosphates.

Cyclization-Activated Prodrugs: N-(Substituted 2-hydroxyphenyl and 2-hydroxypropyl)carbamates Based on Ring-Opened Derivatives of Active Benzoxazolones and Oxazolidinones as Mutual Prodrugs of Acetaminophen

N-(Substituted 2-hydroxyphenyl)- and N-(substituted 2-hydroxypropyl)carbamates based on masked active benzoxazolones (model A) and oxazolidinones (model B), respectively, were synthesized and evaluated as potential drug delivery systems.A series of alkyl and aryl N-(5-chloro-2-hydroxyphenyl)carbamates 1 related to model A was prepared.These are open drugs of the skeletal muscle relaxant chlorzoxazone.The corresponding 4-acetamidophenyl ester named chloracetamol is a mutual prodrug of chloroxazone and acetaminophen.Chlorzacetamol and two other mutual prodrugs of active bezoxazolones and acetaminophen were obtained in a two-step process via condensation of 4-acetamidophenyl 1,2,2,2-tetrachloroethyl carbonate with the appropiate anilines.Based on model B, two mutual prodrugs of acetaminophen and active oxazolidinones (metaxalone and mephenoxalone) were similarly obtained using the appropiate amines.All the carbamate prodrugs prepared were found to release the parent drugs in aqueous (pH 6-11) and plasma (pH 7.4) media.The detailed mechanistic study of prodrugs 1 carried out in aqueous medium at 37 deg C shows a change in the Broensted-type relationship log t1/2 vs pKa of the leaving groups ROH: log t1/2 = 0.46pKa - 3.55 for aryl and trihalogenoethyl esters and log t1/2 = 1.46pKa - 16.03 for alkyl esters.This change is consistent with a cyclization mechanism involving a change in the rate-limiting step from formation of a cyclic tetrahedral intermediate (step k1) to departure of the leaving group ROH (step k2) when the leaving group ability decreases.This mechanism occurs for all the prodrugs related to model A.Regeneration of the parent drugs from mutual prodrugs related to model B takes place by means of a rate-limiting elimination-addition reaction (E1cB mechanism).This affords acetaminophen and the corresponding 2-hydroxypropyl isocyanate intermediates which cyclize at any pH to the corresponding oxazolidinone drugs.As opposed to model A, the rates of hydrolysis of mutual prodrugs of model B clearly exhibit a catalytic role of the plasma.It is concluded from the plasma studies that the carbamate substrates can be enzymatically transformed into potent electrophiles, i.e., isocyanates.In the case of the present study, the prodrugs are 2-hydroxycarbamates for which the propinquity of the hydroxyl residue and the isocyanate group enforces a cyclization reaction.This mechanistic particularity precludes their potential toxicity in terms of potent electrophiles capable of modifying critical macromolecules.

Hydrolysis of Nitrite Esters: Putative Intermediates in the Biotransformation of Organic Nitrates

Study and comparison of the pH-independent hydrolysis of eight alkyl nitrites shows 3-nitroso-1,2-glyceryl dinitrate, a putative intermediate in the biotransformation of glyceryl trinitrate, to be unexpectedly reactive and too labile to be detected as a biotransformation intermediate in aqueous solution, suggesting a role for neighbouring group participation by the β-nitrate group.

Evidence for a concerted mechanism in the solvolysis of phenyldimethylsilyl ethers

The trifluoroethoxide-catalyzed trifluoroethanolysis and the hydroxide-catalyzed hydrolysis of a series of phenyldimethylsilyl ethers were examined. A Bronsted plot of the logarithm of the second-order rate constant KTFE for reaction with trifluoroethanol against the pKLG is not linear. The nonlinear plot might be taken as evidence for a change in rate-determining step of a reaction that proceeds through a pentavalent intermediate. However, the Bronsted plot for the hydroxide-catalyzed hydrolysis, where all the leaving groups are of lower pKa than hydroxide, has an identical shape as the Bronsted plot for the trifluoroethanolysis reaction. Therefore, the unusual shape of the Bronsted plots is not due to a change in rate-determining step. It is suggested that the results are most consistent with a one-step concerted mechanism and not with a mechanism involving a pentavalent intermediate.

General base catalysis of ester hydrolysis

The hydrolysis of alkyl formates with leaving groups in the range pKa = 12-16 is catalyzed by substituted acetate anions. There is an increase in the Br?nsted β value for general base catalysis with decreasing pKa of the leaving alcohol and a complementary increase in -β1g with decreasing pKa of the catalyzing base, both of which are consistent with a value of pxy = ?β/-pK1g = ?β1g/-?pKBH ? 0.11. This result supports a class n mechanism of general base catalysis, in which a proton is abstracted from the nucleophilic water molecule by the base catalyst in the transition state; it is not consistent with the kinetically equivalent class e mechanism of electrophilic catalysis by general acids of a reaction with hydroxide ion, by proton donation to the leaving alcohol. Solvent deuterium isotope effects in the range kH2O/kD2O = 3.6-5.3 for the buffer-independent reaction and 2.5-2.8 for catalysis by CHaCOO- support concerted proton transfer and O-C bond formation. The secondary isotope effect for catalysis of the hydrolysis of LCOOMe by acetate ion is kD/kH = 1.05. Both nucleophilic and general base mechanisms of catalysis by acetate anions are observed for the hydrolysis of substituted phenyl formates with leaving groups of pKa = 7.1-10.1. A small value of β = 0.12 for general base catalysis of the hydrolysis of phenyl formate and p-methylphenyl formate represents catalysis of the addition of water by hydrogen bonding of water to the base catalyst. On the other hand, a larger value of β = 0.35 and a decrease in kH2O/kD2O to 1.2 were observed for general base catalysis of the hydrolysis of p-nitrophenyl formate. It is suggested that the increase in β with decreasing pK1g (an apparent "anti-Hammond effect") may be accounted for by a change in mechanism, from catalysis of a stepwise reaction of phenyl and p-methylphenyl formates to concerted general base catalysis of formyl transfer to water for the reaction of p-nitrophenyl formate.

Reactivity of Nucleophilic Nitrogen Compounds towards the Nitroso Group

We discuss the reactivity of 43 nucleophilic nitrogen compounds towards the nitroso group of N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS), and in some cases with alkyl nitrites.The series of nucleophiles considered is structurally very varied, includes members exhibiting the alpha effect, and covers 8 pKa units and a range of reactivities of almost five orders of magnitude.The values of solvent isotope effects and activation parameters have been measured and throw light on the structure of the transition states involved.Reactivities do not correlate well with thebasicity of the nucleophile, largely owing to the behaviour of primary amines, ammonia and nucleophiles with an alpha effect.Application of the curve crossing model suggests a relationship with vertical ionization potentials.The relationship with Ritchie's N+ scale is discussed, and interesting correlations with the reactivities of the same nucleophiles in various other chemical processes are noted.

Laser Photolysis/Laser-Induced Fluorescence Studies of the Reaction of OH with 1,1-Dichloroethane over an Extended Temperature Range

Absolute rate coefficients are determined for the gas-phase reaction of OH radicals with 1,1-dichloroethane over an extended temperature range using a laser photolysis/laser-induced fluorescence technique.Experiments were performed in a flow system at a total pressure of 740 +/- 10 Torr using He as diluent and carrier gas.The rate coefficients, obtained over the temperature range 294-800 K, exhibited pronounced non-Arrhenius behavior and were best described by the modified Arrhenius equation k(T)=(8.29 +/- 0.36) x 10-14(T/300)2.67exp cm3 molecule-1 s-1.Comparison of the data with one previous room-temperature measurement is presented.The temperature dependence of the data is compared with empirical and transition-state model calculations.The influence of C-H bond energy and Cl substitution is discussed.