99-91-2

Hazards Identification

Pictogram(s):

Signal:

Warning

GHS Hazard Statements:

H302: Harmful if swallowed [Warning Acute toxicity, oral]

Precautionary Statement Codes:

P264, P270, P301+P317, P330, and P501

Hazard Classes and Categories:

Acute toxicity (Oral) - Category 4

Hazards Summary:

Highly irritating to eyes; [Merck Index] May cause allergic contact dermatitis; [HSDB] An irritant; Effects in high-dose animal studies include lacrimation and acute pulmonary edema; [MSDSonline] See alpha-Chloroacetophenone.

Usage

Uses

Used in Law Enforcement:
4'-Chloroacetophenone is used as a tear gas for riot control, serving as an effective means to manage and disperse crowds during civil unrest or protests. Its ability to cause intense irritation to the eyes, respiratory tract, and skin makes it a potent agent for controlling large groups of people.
Used in Personal Defense:
In addition to its role in riot control, 4'-Chloroacetophenone is also utilized as a component of chemical mace or pepper spray. It is employed for self-defense purposes against small groups or individuals, providing a non-lethal means of protection. When used in this context, 4'-Chloroacetophenone can incapacitate an aggressor temporarily, allowing the user to escape or seek assistance.

Synthesis Reference(s)

The Journal of Organic Chemistry, 44, p. 2568, 1979 DOI: 10.1021/jo01328a051Tetrahedron Letters, 42, p. 265, 2001 DOI: 10.1016/S0040-4039(00)01935-3Synthetic Communications, 25, p. 2261, 1995 DOI: 10.1080/00397919508011781

Safety Profile

Poison by intraperitoneal route. Moderately toxic by ingestion. A powerful irritant and lachrymator. Human systemic effects by inhalation: lachrymation and unspecified effects on the eye and sense of smell. Combustible when exposed to heat or flame. To fight fire, use water, foam, alcohol foam, dry chemical. When heated to decomposition or on contact with water or steam it emits toxic fumes of Cl-

Upstream product

• 1073-67-2 4-vinylbenzyl chloride 
• 107-29-9 Acetaldehyde oxime 
• 17333-85-6 4-chlorophenyldiazonium salt 
• 1615-02-7 p-chlorocinnamic acid 
• 3710-84-7 N-ethyl-N-hydroxy-ethanamine 
• 127-19-5 N,N-dimethyl acetamide 
• 14774-78-8 4-chlorophenyl lithium 
• 3391-10-4 1-(p-chlorophenyl)ethyl alcohol 
• 24045-70-3 diethyl 2-(4-chlorobenzoyl)malonate 
• 17589-68-3 3-(4-chlorophenyl)-3-oxopropanoic acid 
• 108-24-7 acetic anhydride 
• 108-90-7 chlorobenzene 
• 99187-99-2 2-(4-chlorophenyl)butane-2,3-diol 
• 546-67-8 lead(IV) tetraacetate 

Downstream Products

• 42945-85-7 2-(4-chlorophenyl)-1-(morpholin-4-yl)-ethanethione 
• 28561-06-0 1-(4-chloro-phenyl)-1-pyridin-4-yl-ethanol 
• 197512-40-6 1-(4-chlorophenyl)-1-(pyridin-2-yl)ethan-1-ol 
• 105688-33-3 1-[2-(4-chloro-phenyl)-2-oxo-ethyl]-pyridinium iodide 
• 5337-52-0 (E)-1-(4-chlorophenyl)-3-(pyridin-2-yl)prop-2-en-1-one 
• 14385-65-0 (2E)-1-(4-chlorophenyl)-3-(2-furyl)prop-2-en-1-one 
• 351332-56-4 2-(4-chlorophenyl)-6-methylquinoline-4-carboxylic acid 
• 69538-64-3 (E)-3-(benzo[d][1,3]dioxol-5-yl)-1-(4-chlorophenyl)prop-2-en-1-one 
• 124930-93-4 8-chloro-2-(4-chlorophenyl)cinchoninic acid 
• 5466-31-9 2-(4-chlorophenyl)quinoline-4-carboxylic acid 
• 23241-13-6 3-(2-(4-chlorophenyl)-2-oxoethyl)-3-hydroxyindolin-2-one 
• 351327-32-7 6-bromo-2-(4-chloro-phenyl)-quinoline-4-carboxylic acid 
• 85460-65-7 (E)-3-(2-chlorophenyl)-1-(4-chlorophenyl)prop-2-en-1-one 
• 132971-93-8 (E)-1-(4-chlorophenyl)-3-(2-hydroxyphenyl)prop-2-en-1-one 

Relevant academic research and scientific papers

Catalytic oxidation of alcohols by a novel manganese Schiff base ligand derived from salicylaldehyd and l-Phenylalanine in ionic liquids

A selective oxidation of alcohols to corresponding carbonyl compounds in ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([bmim]BF4) was achieved by using a novel salicylaldehyd amino acid Schiff base manganese ligand. The catalytic s

Visible light-mediated, high-efficiency oxidation of benzyl to acetophenone catalyzed by fluorescein

An environmentally friendly aerobic oxidation of benzyl C(sp3)-H bonds to ketones via selective oxidation catalysis was developed. Fluorescein is an efficient photocatalyst with excellent chemical selectivity. The reaction has a wide substrate scope, and a successful gram-scale experiment demonstrated its potential industrial utility.

Stepwise benzylic oxygenation via uranyl-photocatalysis

Stepwise oxygenation at the benzylic position (1°, 2°, 3°) of aromatic molecules was comprehensively established under ambient conditions via uranyl photocatalysis to produce carboxylic acids, ketones, and alcohols, respectively. The accuracy of the stepwise oxygenation was ensured by the tunability of catalytic activity in uranyl photocatalysis, which was adjusted by solvents and additives demonstrated through Stern–Volmer analysis. Hydrogen atom transfer between the benzylic position and the uranyl catalyst facilitated oxygenation, further confirmed by kinetic studies. Considerably improved efficiency of flow operation demonstrated the potential for industrial synthetic application.

Selective Activation of Unstrained C(O)-C Bond in Ketone Suzuki-Miyaura Coupling Reaction Enabled by Hydride-Transfer Strategy

A Rh(I)-catalyzed ketone Suzuki-Miyaura coupling reaction of benzylacetone with arylboronic acid is developed. Selective C(O)-C bond activation, which employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, occurs on the alkyl chain containing a β-position hydrogen. A series of acetophenone products were obtained in yields up to 75%.

Exploration of highly electron-rich manganese complexes in enantioselective oxidation catalysis; A focus on enantioselective benzylic oxidation

The direct enantioselective hydroxylation of benzylic C-H bonds to form chiral benzylic alcohols represents a challenging transformation. Herein, we report on the exploration of new biologically inspired manganese and iron complexes bearing highly electron-rich aminopyridine ligands containing 4-pyrrolidinopyridine moieties ((S,S)-1, (R,R)-1, 2 and 5) in combination with chiral bis-pyrrolidine and N,N-cyclohexanediamine backbones in enantioselective oxidation catalysis with aqueous H2O2. The current manganese complexes outperform the analogous manganese complexes containing 4-dimethylaminopyridine moieties (3 and 4) in benzylic oxidation reactions in terms of alcohol yield while keeping similar ee values (～60% ee), which is attributed to the higher basicity of the 4-pyrrolidinopyridine group. A detailed investigation of different carboxylic acid additives in enantioselective benzylic oxidation provides new insights into how to rationally enhance enantioselectivities by means of proper tuning of the environment around the catalytic active site, and has resulted in the selection of Boc-l-Tert-leucine as the preferred additive. Using these optimized conditions, manganese complex 2 was shown to be effective in the enantioselective benzylic oxidation of a series of arylalkane substrates with up to 50% alcohol yield and 62% product ee. A final set of experiments also highlights the use of the new 4-pyrrolidinopyridine-based complexes in the asymmetric epoxidation of olefins (up to 98% epoxide yield and >99% ee).

Promoting charge separation in donor-acceptor conjugated microporous polymers: Via cyanation for the photocatalytic reductive dehalogenation of chlorides

Conjugated microporous polymers (CMPs) have emerged as promising heterogeneous photocatalysts for organic transformations owing to their structural designability and functional versatility. However, limited by the insufficient separation of the photo-generated excitons, their photocatalytic efficiency falls far short of expectations. Herein, we demonstrate a cyanation strategy to promote charge carrier separation in CMPs by selectively incorporating carbazole and cyano groups as electron-donating and electron-withdrawing units, respectively. The resulting CMPs feature π-extended donor (D)-acceptor (A) conjugation structures endowing them with distinct semiconducting properties, in which the efficient charge separation and transfer and wide visible-light absorption are facilitated. Compared to the cyano-free counterpart, the cyano-functionalized CMPs showed superior photocatalytic efficiency as exemplified by photocatalytic reductive dehalogenation of chlorides. More prominently, full recyclability of the designed CMPs as well as catalytic activity for at least ten runs without the loss of catalytic performance in photocatalytic reductive dehalogenation of chlorides demonstrated their robustness and sustainability. This journal is

Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy

Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.

PhSe(O)OH/NHPI-catalyzed oxidative deoximation reaction using air as oxidant

A novel oxidative deoximation method was developed in this article. Compared with the reported organoselenium-catalyzed oxidative deoximation reaction, this reaction employed N-hydroxyphthalimide (NHPI) as the co-catalyst, so that the oxidative deoximation reaction could utilize air as oxidant in the green DMC solvent under mild reaction conditions. Control experiments and X-ray photoelectron spectroscopy (XPS) analysis results indicated that NHPI was essential for activating the catalytic organoselenium species. It could accelerate the activation of molecular oxygen in air to promote the reaction process. The reaction can avoid metal residues in product and is of potential application values in pharmaceutical industry due to the transition metal-free process.

PhIO-Mediated oxidative dethioacetalization/dethioketalization under water-free conditions

Treatment of thioacetals and thioketals with iodosobenzene in anhydrous DCM conveniently afforded the corresponding carbonyl compounds in high yields under water-free conditions. The mechanistic studies indicate that this dethioacetalization/dethioketalization process does not need water and the oxygen of the carbonyl products comes from the hypervalent iodine reagent.

Catalytic alcohol oxidation using cationic Schiff base manganeseIII complexes with flexible diamino bridge

Four Schiff base manganese(III) complexes with derivatives of [(R,R)-N,N’-bis(salicy1idene)-1,2-cyclohexanediaminato)] including substituents on salicylaldehyde such as 3-methoxy, 3,5-di-tert-butyl and 3,5-chloro were synthesized and characterized using a combination of IR, UV–Vis, and HR ESI-MS techniques. The catalytic activity of these complexes was tested in the oxidation of 1-phenylethanol to acetophenone, revealing very good performances for all of the four manganese complexes. The catalytic reactions were carried out in the presence of tert-butyl hydroperoxide (TBHP) as oxidant and imidazole as co-catalyst. Complex Mn-4, bearing electron withdrawing [(R,R)-N,N’-bis(3,5-di-chloro-salicylidene)-1,2-cyclohexanediaminato)] ligand was found to be the most stable of the tested Mn(III) complexes and was selected for the oxidation of several primary and secondary alcohols.