99-91-2

Basic information

• Product Name: 4'-Chloroacetophenone
• Synonyms: 1-(4-chlorophenyl)-ethanon;1-(4-chlorophenyl)ethanone[qr];4’-chloro-acetophenon;4-acetylchlorobenzene;4-chloroacetophenone[qr];4-chlorophenylmethylketone;Acetophenone, 4'-chloro-;acetophenone,4-chloro-[qr]
• CAS NO: 99-91-2
• Molecular Formula: C₈H₇ClO
• Molecular Weight: 154.59
• EINECS: 202-800-7
• Product Categories: Chlorobenzene Series;Acetophenone Series;FINE Chemical & INTERMEDIATES;Aromatic Acetophenones & Derivatives (substituted);Organics;C7 to C8;Carbonyl Compounds;Ketones
• Mol File: 99-91-2.mol

Chemical Properties

• Melting Point: 74-76 °C(lit.)
• Boiling Point: 232 °C(lit.)
• Flash Point: 194 °F
• Appearance: Clear colorless to yellow/Liquid After Melting
• Density: 1.192 g/mL at 25 °C(lit.)
• Vapor Pressure: 8 mm Hg ( 90 °C)
• Refractive Index: n20/D 1.554(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: 111mg/l (slow decomposition)
• Water Solubility: 111 mg/L (25 ºC)
• Merck: 14,2116
• BRN: 386014
• CAS DataBase Reference: 4'-Chloroacetophenone(CAS DataBase Reference)
• NIST Chemistry Reference: 4'-Chloroacetophenone(99-91-2)
• EPA Substance Registry System: 4'-Chloroacetophenone(99-91-2)

Safety Data

• Hazard Codes: T+,Xn
• Statements: 22-26-37/38-41-36/37/38-36/37
• Safety Statements: 26-28-36/37/39-45-28A-36
• RIDADR: UN 3416 6.1/PG 2
• WGK Germany: 3
• RTECS: KM5600000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 99-91-2(Hazardous Substances Data)

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

• 107-29-9 Acetaldehyde oxime 
• 17333-85-6 4-chlorophenyldiazonium salt 
• 3710-84-7 N-ethyl-N-hydroxy-ethanamine 
• 127-19-5 N,N-dimethyl acetamide 
• 14774-78-8 4-chlorophenyl lithium 
• 24045-70-3 diethyl 2-(4-chlorobenzoyl)malonate 
• 99187-99-2 2-(4-chlorophenyl)butane-2,3-diol 
• 546-67-8 lead(IV) tetraacetate 
• 64-19-7 acetic acid 
• 75-36-5 acetyl chloride 
• 108-90-7 chlorobenzene 
• 562-90-3 tetraacetoxysilane 
• 591-86-6 acetaldehyde semicarbazone 
• 99-92-3 p-aminobenzophenone 

Downstream Products

• 42945-85-7 2-(4-chlorophenyl)-1-(morpholin-4-yl)-ethanethione 
• 7469-98-9 1,4-bis-[3-(4-chloro-phenyl)-3-oxo-propyl]-piperazine; dihydrochloride 
• 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 
• 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 
• 6302-55-2 1-(4'-chlorophenyl)-1,3-butanedione 
• 19672-63-0 (2E)-1-(4-chlorophenyl)-3-(4-methylphenyl)prop-2-en-1-one 
• 21399-27-9 2,4,6-tris(4-chlorophenyl)pyridine 
• 20725-25-1 1,3-bis(4-chlorophenyl)prop-2-en-1-one 

Relevant articles and documents

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%.

Efficient Aliphatic C-H Oxidation and C═C Epoxidation Catalyzed by Porous Organic Polymer-Supported Single-Site Manganese Catalysts

Bioinspired manganese complexes have emerged over recent decades as attractive catalysts for a number of selective oxidation reactions. However, these catalysts still suffer from oxidative degradation. In the present study, we prepared a series of porous Mn-N4 catalysts in which the catalytic units are embedded in the skeleton of porous organic polymers (POPs). These POP-based manganese catalysts demonstrated high reactivity in the oxidation of aliphatic C-H bonds and the asymmetric epoxidation of olefins. Furthermore, these catalysts could be readily recycled and reused due to their heterogeneous nature. Morphological characterization revealed that the Mn-N4 complex was individually distributed over a porous polymer network. Remarkably, the nature of the single-site catalyst prevented oxidative degradation during the reaction. The present work has thus developed a successful approach for bioinspired single-site manganese catalysts in which the oxidation reaction is confined to a specific channel in an enzyme-like mode.

Visible-light photocatalytic selective oxidation of C(sp3)-H bonds by anion-cation dual-metal-site nanoscale localized carbon nitride

Selective oxidation of C(sp3)-H bonds to carbonyl groups by abstracting H with a photoinduced highly active oxygen radical is an effective method used to give high value products. Here, we report a heterogeneous photocatalytic alkanes C-H bonds oxidation method under the irradiation of visible light (λ= 425 nm) at ambient temperature using an anion-cation dual-metal-site modulated carbon nitride. The optimized cation (C) of Fe3+or Ni2+, with an anion (A) of phosphotungstate (PW123?) constitutes the nanoscale dual-metal-site (DMS). With a Fe-PW12dual-metal-site as a model (FePW), we demonstrate a A-C DMS nanoscale localized carbon nitride (A-C/g-C3N4) exhibiting a highly enhanced photocatalytic activity with a high product yield (86% conversion), selectivity (up to 99%), and a wide functional group tolerance (52 examples). The carbon nitride performs the roles of both the visible light response, and improves the selectivity for the oxidation of C(sp3)-H bonds to carbonyl groups, along with the function of A-C DMS in promoting product yield. Mechanistic studies indicate that this reaction follows a radical pathway catalyzed by a photogenerated electron and hole on A-C/g-C3N4that is mediated by thetBuO˙ andtBuOO˙ radicals. Notably, a 10 g scale reaction was successfully achieved for alkane photocatalytic oxidation to the corresponding product with a good yield (80% conversion), and high selectivity (95%) under natural sunlight at ambient temperature. In addition, this A-C/g-C3N4photocatalyst is highly robust and can be reused at least six times and the activity is maintained.

Ferric ion concentration-controlled aerobic photo-oxidation of benzylic C–H bond with high selectivity and conversion

A Fe(III)-promoted highly selective photo-oxidation of benzylic C–H bond delivering relative carbonyl products is reported. By altering the concentration of ferric salt, methylarenes can be selectively oxidized under UV irradiation to furnish aromatic aldehydes or acids, respectively. By this protocol, the oxidation of ethylarenes provides the corresponding acetophenones. The reaction is inferred to involve divergent pathways in different concentrations of catalyst for the alternative selectivity between aldehydes and aicds. The reusable catalyst, high conversion and selectivity make this oxidation a green and economic protocol for the synthesis of aromatic carbonyl compounds.

Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis

A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.

HCl-Catalyzed Aerobic Oxidation of Alkylarenes to Carbonyls

The construction of C?O bonds through C?H bond functionalization remains fundamentally challenging. Here, a practical chlorine radical-mediated aerobic oxidation of alkylarenes to carbonyls was developed. This protocol employed commercially available HCl as a hydrogen atom transfer (HAT) reagent and air as a sustainable oxidant. In addition, this process exhibited excellent functional group tolerance and a broad substrate scope without the requirement for external metal and oxidants. The mechanistic hypothesis was supported by radical trapping, 18O labeling, and control experiments.

Selective Electrochemical Oxygenation of Alkylarenes to Carbonyls

An efficient electrochemical method for benzylic C(sp3)-H bond oxidation has been developed. A variety of methylarenes, methylheteroarenes, and benzylic (hetero)methylenes could be converted into the desired aryl aldehydes and aryl ketones in moderate to excellent yields in an undivided cell, using O2 as the oxygen source and lutidinium perchlorate as an electrolyte. On the basis of cyclic voltammetry studies, 18O labeling experiments, and radical trapping experiments, a possible single-electron transfer mechanism has been proposed for the electrooxidation reaction.