1794-86-1

Basic information

• Product Name: dichloroformoxine
• Synonyms: dichloroformoxine;Dichloroformaldehyde oxime;Dichloroformaldoxime;Dichloroformoxime;Dichloromethanone oxime;Hydroxycarbonimidic dichloride;Phosgene oxime;N-(dichloromethylidene)hydroxylamine
• CAS NO: 1794-86-1
• Molecular Formula: CHCl₂NO
• Molecular Weight: 113.93
• Mol File: 1794-86-1.mol
• Article Data: 10

Chemical Properties

• Melting Point: 39-40 °C
• Boiling Point: 185.1°C at 760 mmHg
• Flash Point: 65.7°C
• Appearance: /
• Density: 1.66g/cm³
• Vapor Pressure: 0.201mmHg at 25°C
• Refractive Index: 1.503
• PKA: 7.70±0.11(Predicted)
• CAS DataBase Reference: dichloroformoxine(CAS DataBase Reference)
• NIST Chemistry Reference: dichloroformoxine(1794-86-1)
• EPA Substance Registry System: dichloroformoxine(1794-86-1)

Safety Data

• Hazardous Substances Data: 1794-86-1(Hazardous Substances Data)

Usage

Description

Phosgene oxime is a colourless solid or yellowish-brown liquid with a disagreeable penetrating odour. Pure phosgene oxime is a colourless, crystalline solid; the munitions grade compound is a yellowish-brown liquid. Phosgene oxime is soluble in water and organic solvents, but hydrolyses rapidly, and especially in the presence of alkali. Chemically similar to but more reactive than an amide. Incompatible with strong acids and bases, and especially incompatible with strong reducing agents such as hydrides. It is also incompatible with strongly oxidising acids, peroxides, and hydroperoxides. Phosgene oxime is a very severe blistering agent. Both the liquid and the solid can give off vapours at ambient temperatures. Phosgene oxime was developed as a potential chemical warfare agent but has never been known to be used on the battlefield. Phosgene oxime (CX) is an urticant or nettle agent causing instant intolerable pain, erythema, wheals, and urticaria. It is very corrosive, capable of causing extensive tissue damage. Phosgene oxime was first produced by the Germans in 1929 as a possible warfare agent. The mechanism of action is not fully understood but the lesions produced in the skin are similar to those caused by a strong acid. Phosgene oxime will penetrate ordinary clothing and surgical gear.

Chemical Properties

Phosgene oxime (military designation CX) is a non-combustible urticant (nettle agent, blister agent) with a short (seconds to minutes) latency period. CX is a colorless, low-melting point (crystalline, white powder) solid or as a liquid (liquid above 39C; solid below 35C). On hot days (or at body temperature) it can appear as a yellowishbrown liquid. It has a high vapor pressure (the vapor pressure of the solid is high enough to produce symptoms), slowly decomposes at normal temperatures. It has an intense, disagreeable,penetrating, and violently irritating, peppery odor. Odor detectable at less than 0.3 ppm.

Uses

There are no commercial or beneficial uses of phosgene oxime. It was developed and produced solely as a chemical warfare agent, but has never been used on the battlefield.

General Description

Colorless liquid, odorless to fruity.

Reactivity Profile

dichloroformoxine is an oxime. Chemically similar to, but more reactive than an amide. Incompatible with strong acids and bases, and especially incompatible with strong reducing agents such as hydrides. Also incompatible with strongly oxidizing acids, peroxides, and hydroperoxides.

Health Hazard

Median lethal dose (mg-min/m3): 3200 (inhaled). Median incapacitating dose: Very low. Eye/skin toxicity: Powerful irritant to eyes and nose; liquid corrosive to skin. Rate of action: Immediate effects on contact. Physiological action: Violently irritates mucous membranes, eyes and nose; forms wheals rapidly. (ANSER)

Potential Exposure

There’s no industrial use for Phosgene oxime (CX) and because of its extreme instability, the pure material is not likely to be used in military operations. CX is especially dangerous when mixed with other chemicals such as nerve agents. It burns away the skin making it more permeable to any other “added” agents. No other chemical agent is capable of producing immediate extreme pain followed by rapid local tissue death (necrosis). Post World War II studies indicate that concentrations below 8% cause no or inconsistent effects.

Environmental Fate

Phosgene oxime does not accumulate in the soil since both phosgene oxime and the parent compound of phosgene have been shown to be highly unstable in the environment. Small amounts which may be present can vaporize into the air or be degraded by soil bacteria. Once in vapor form, phosgene oxime remains in vapor form and will be inactivated by compounds in the atmosphere or broken down by bacteria. There is no evidence that phosgene oxime will accumulate in groundwater. Phosgene oxime is fairly soluble in water and if exposed to soil moisture may rapidly decompose to CO2, HCl, and hydroxy amine hydrochloride.

Shipping

UN2811 (solid)/UN2810 (liquid) Toxic solids or liquids, organic, n.o.s., Hazard Class: 6.1; Labels: 6.1Poisonous materials, Technical Name Required. Military driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.

Toxicity evaluation

The molecular mechanism of phosgene oxime toxicity is unknown. Phosgene oxime is the least well studied of all vesicant/urticant compounds but possible mechanisms may involve the actions of (1) necrotizing effects of chlorine, (2) direct toxic effects of oxime, and/or (3) the actions of carbonyl groups on the target tissue. One hypothesis is that phosgene oxime toxicity can be broken down into two mechanisms. First is a direct mechanism which will involve direct enzymatic inactivation, cell death, corrosive injury, and rapid destruction of the tissue that phosgene oxime has contacted. Secondarily, there are a series of indirect mechanisms that may increase tissue injury. There is activation of alveolar macrophages, recruitment of neutrophils to the damage site, release of hydrogen peroxide, and then delayed disuse injury following the edema associated with phosgene oxime exposure.

Incompatibilities

Phosgene oxime (CX) is among the most important halogenated oximes. CX reacts with water, sweat, and heat, forming hydrochloric acid. CX may be an oxidizer, and it may ignite combustibles, e.g., wood, paper, oil, or clothing). CX is incompatible with strong acids and bases; hydrides and other strong reducing agents such as hydrides; strong oxidizing acids, peroxides, and hydroperoxides. Not hydrolyzed by dilute acids; reacts violently in basic solutions forming carbon dioxide, hydrogen chloride, and hydroxylamine. Hydrolysis products include HCl and methylarsenic oxide. CX quickly penetrates rubber and clothing. Traces of many metals cause it to decompose; however, it corrodes most metals. Oximes are chemically similar to, but more reactive than amides. Incompatible with strong acids and bases, and especially incompatible with strong reducing agents such as hydrideds and active metals. Also incompatible with strongly oxidizing acids, peroxides, and hydroperoxides. CX decomposes when in contact with many metals; it is corrosive to most metals, and contact with metals may evolve flammable hydrogen gas.

Waste Disposal

Seek expert advice from armed services (see Reference section), Center for Disease Control headquarters in Atlanta, Ga.

InChI:InChI=1/CHCl2NO/c2-1(3)4-5/h5H

Synthetic route

Chloronitroacetyl chloride (85915-53-3) → dichloroformoxime (1794-86-1)

Conditions	Yield
With urea In diethyl ether for 0.5h; Heating; further reagents (C6H11NH)2CO, (MeNH)2CO, thiourea, (PhNH)2CO;	75%

mercury(II) fulminate → 3,4-dichloro-1,2,5-oxadiazole-N-oxide (34698-60-7) + dichloroformoxime (1794-86-1)

Conditions	Yield
With chlorine In water under cooling with ice-water Cl2 is led into the suspension; dichlorofuroxane isolated as oil; dichlorofuroxim extracted with ether;	A n/a B 40%
With Cl2 In water under cooling with ice-water Cl2 is led into the suspension; dichlorofuroxane isolated as oil; dichlorofuroxim extracted with ether;	A n/a B 40%
With chlorine In hydrogenchloride
With Cl2 In hydrogenchloride

stannane (7440-31-5) + chloropicrin (76-06-2) → dichloroformoxime (1794-86-1)

Conditions	Yield
With tin In acetonitrile	16.8%

trichloronitrosomethane (3711-49-7) → dichloroformoxime (1794-86-1)

Conditions	Yield
With hydrogenchloride; diethyl ether; tin(ll) chloride
With ethanol; sulfur dioxide; water
With ethanol; hydrogen sulfide
With methanol; hydrogen sulfide
With methanol; aluminium amalgam

bromodichloronitrosomethane (73411-12-8) → dichloroformoxime (1794-86-1)

Conditions	Yield
With methanol; hydrogen sulfide

chloropicrin (76-06-2) → dichloroformoxime (1794-86-1)

Conditions	Yield
With sulfuric acid durch elektrolytische Reduktion an einer Zinnkathode;
With hydrogenchloride; tin; diethyl ether at 0 - 5℃;
(reduction);

chloropicrin (76-06-2) → dichloroformoxime (1794-86-1) + N-Methylhydroxylamine (593-77-1) + trichloronitrosomethane (3711-49-7) + methylamine (74-89-5)

Conditions	Yield
Bei der elektrolytischen Reduktion entstehen je nach den Bedingungen wechselnde Menge;

dichloro-dinitro-methane (1587-41-3) → dichloroformoxime (1794-86-1)

Conditions	Yield
With hydrogenchloride; tin; diethyl ether at 0 - 5℃;

mercury fulminate (92114-96-0) → dichloroformoxime (1794-86-1)

Conditions	Yield
With water; chlorine
With hydrogenchloride; chlorine
With chloroethane; chlorine
With sodium hypochlorite

sodium cyanate (15736-98-8) → dichloroformoxime (1794-86-1)

Conditions	Yield
With sulfuric acid; water; chlorine at 0℃;

nitromethane (75-52-5) → dichloroformoxime (1794-86-1)

Conditions	Yield
With chlorine

hydroxyiminoacetic acid (3545-80-0) → dichloroformoxime (1794-86-1)

Conditions	Yield
With N-chloro-succinimide In 1,2-dimethoxyethane for 0.166667h; Heating;
With N-chloro-succinimide In 1,2-dimethoxyethane Heating;
With N-chloro-succinimide In 1,2-dimethoxyethane at 55 - 110℃;

Glyoxilic acid (298-12-4) → dichloroformoxime (1794-86-1)

Conditions	Yield
With hydroxylamine hydrochloride; chlorine; sodium hydrogencarbonate 1.) water, 18 h; Multistep reaction;

glyoxylic acid aldoxime (168208-95-5) → dichloroformoxime (1794-86-1)

Conditions	Yield
With N-chloro-succinimide In 1,2-dimethoxyethane Heating;

pyruvohydroximoyl chloride (5471-68-1) + water (7732-18-5) + chlorine (7782-50-5) → dichloroformoxime (1794-86-1) + chloropicrin (76-06-2)

Conditions	Yield
at 10 - 20℃;

1-chloro-1-hydroxyimino-acetone → dichloroformoxime (1794-86-1)

Conditions	Yield
With water; chlorine at 10 - 20℃;

methanol (67-56-1) + trichloronitrosomethane (3711-49-7) + hydrogen sulfide (7783-06-4) → dichloroformoxime (1794-86-1)

ethanol (64-17-5) + trichloronitrosomethane (3711-49-7) + hydrogen sulfide (7783-06-4) → dichloroformoxime (1794-86-1)

ethanol (64-17-5) + trichloronitrosomethane (3711-49-7) + amalgamated aluminium → dichloroformoxime (1794-86-1)

hydrogenchloride (7647-01-0) + diethyl ether (60-29-7) + chloropicrin (76-06-2) + tin → dichloroformoxime (1794-86-1)

Conditions	Yield
at 0 - 5℃;

fulminic acid (51060-05-0) → dichloroformoxime (1794-86-1)

Conditions	Yield
With chlorine In water
With chlorine In diethyl ether -80°C;
With chlorine In further solvent(s) in ethyl chloride;

dichloroformoxime (1794-86-1) + 1-copper(I) (4-ethylphenyl)ethyne → 3-chloro-5-(4-ethylphenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.616667h;	97%

dichloroformoxime (1794-86-1) + copper(I) 4-methoxyphenylacetylenide (48121-13-7) → 3-chloro-5-(4-methoxyphenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.783333h;	95%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-chlorophenyl)ethyne (49748-64-3) → 3-chloro-5-(4-chlorophenyl)isoxazole (56045-68-2)

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.783333h;	95%

dichloroformoxime (1794-86-1) + C7H11Cu (1371569-77-5) → 3-chloro-4-iodo-5-isopentylisoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	94%

copper(I) phenylacetylenide (13146-23-1) + dichloroformoxime (1794-86-1) → 3-chloro-4-iodo-5-phenylisoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h; Concentration; Temperature;	94%

dichloroformoxime (1794-86-1) + copper(I) cyclohexylethynylide (78630-29-2) → 3-chloro-5-cyclohexylisoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.5h;	93%

dichloroformoxime (1794-86-1) + 1-copper(I) (3-methylphenyl)ethyne (99254-92-9) → 3-chloro-5-(3-methylphenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.683333h;	93%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-chlorophenyl)ethyne (49748-64-3) → 3-chloro-4-iodo-5-(4-chlorophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	93%

dichloroformoxime (1794-86-1) + C7H11CuO → 3-chloro-4-iodo-5-(tert-butoxymethyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	93%

copper(I) phenylacetylenide (13146-23-1) + dichloroformoxime (1794-86-1) → 3-chloro-5-phenylisoxazole (31329-61-0)

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 1h;	92%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-fluorophenyl)ethyne → 3-chloro-4-iodo-5-(4-fluorophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	92%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-bromophenyl)ethyne (118520-70-0) → 3-chloro-5-(4-bromophenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.583333h;	91%

dichloroformoxime (1794-86-1) + copper(I) (2-fluorophenyl)acetylide → 3-chloro-4-iodo-5-(2-fluorophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	91%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-bromophenyl)ethyne (118520-70-0) → 3-chloro-4-iodo-5-(4-bromophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	91%

dichloroformoxime (1794-86-1) + 1-copper(I) (2-methylphenyl)ethyne → 3-chloro-5-(2-methylphenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.9h;	90%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-fluorophenyl)ethyne → 3-chloro-5-(4-fluorophenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 1.5h;	90%

dichloroformoxime (1794-86-1) + 1-copper(I) (3-fluorophenyl)ethyne → 3-chloro-4-iodo-5-(3-fluorophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	90%

dichloroformoxime (1794-86-1) + copper(I) (2-fluorophenyl)acetylide → 3-chloro-5-(2-fluorophenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.5h;	89%

dichloroformoxime (1794-86-1) + N-allylacetamide (692-33-1) → 5-<(acetylamino)methyl>-3-chloro-2-isoxazoline (121596-80-3)

Conditions	Yield
With potassium hydrogencarbonate In water; ethyl acetate for 20h;	88%

dichloroformoxime (1794-86-1) + copper(I) hexylacetylenide (54502-24-8) → 3-chloro-4-iodo-5-heptylisoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	87%

dichloroformoxime (1794-86-1) + (p-tolylethynyl)copper (31638-66-1) → 3-chloro-5-(4-methylphenyl)isoxazole (62847-41-0)

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.5h;	85%

dichloroformoxime (1794-86-1) + (p-tolylethynyl)copper (31638-66-1) → 3-chloro-4-iodo-5-(4-tolyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	84%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-nitrophenyl)ethyne (48129-93-7) → 3-chloro-5-(4-nitrophenyl)isoxazole (62847-42-1)

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.55h;	83%

dichloroformoxime (1794-86-1) + 1-copper(I) (4-nitrophenyl)ethyne (48129-93-7) → 3-chloro-4-iodo-5-(4-nitrophenyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	83%

styrene (292638-84-7) + dichloroformoxime (1794-86-1) → butyl 3-(trichlorovinyl)-4,5-dihydroisoxazole-5-carboxylate (62056-52-4)

Conditions	Yield
With potassium hydrogencarbonate In 1,2-dimethoxyethane; water at 25℃; for 12h;	82%
With silver nitrate In tetrahydrofuran at 60 - 65℃; for 0.333333h;	73%
With silver nitrate In tetrahydrofuran at 60 - 65℃; for 0.333333h; Product distribution; Var. alkene;	73%
With sodium carbonate In diethyl ether; water for 26h;	32.02%

dichloroformoxime (1794-86-1) + 1-copper(I) (3-fluorophenyl)ethyne → 3-chloro-5-(3-fluorophenyl)isoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 1.33333h;	82%

dichloroformoxime (1794-86-1) + 1-copper(I) (3-methylphenyl)ethyne (99254-92-9) → 3-chloro-4-iodo-5-(3-tolyl)isoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	82%

dichloroformoxime (1794-86-1) + 1-copper(I)-5-methylhex-1-yne → 3-chloro-5-isopentylisoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.2h;	81%

dichloroformoxime (1794-86-1) + 1-copper(I) cyclopropylethyne → 3-chloro-4-iodo-5-cyclopropylisoxazole

Conditions	Yield
With iodine; sodium hydrogencarbonate In N,N-dimethyl-formamide at 20℃; for 6.16667h;	81%

dichloroformoxime (1794-86-1) + 1-copper(I) cyclopentylethyne → 3-chloro-5-cyclopentylisoxazole

Conditions	Yield
In N,N-dimethyl-formamide at 45℃; for 0.5h;	80%

Upstream product

• 1587-41-3 dichloro-dinitro-methane 
• 15736-98-8 sodium cyanate 
• 3545-80-0 hydroxyiminoacetic acid 
• 168208-95-5 glyoxylic acid aldoxime 
• 5471-68-1 pyruvohydroximoyl chloride 
• 7732-18-5 water 
• 7782-50-5 chlorine 
• 67-56-1 methanol 
• 3711-49-7 trichloronitrosomethane 
• 7783-06-4 hydrogen sulfide 
• 64-17-5 ethanol 
• 7647-01-0 hydrogenchloride 
• 60-29-7 diethyl ether 
• 76-06-2 chloropicrin 

Downstream Products

• 1587-41-3 dichloro-dinitro-methane 
• 5329-29-3 triaminoguanidine hydrochloride 
• 73028-29-2 3-chloro-isoxazole 
• 85559-44-0 (4S,5S)-3-Chloro-5-methyl-4-phenyl-4,5-dihydro-isoxazole 
• 85559-43-9 (4S,5R)-3-Chloro-4-methyl-5-phenyl-4,5-dihydro-isoxazole 
• 124-38-9 carbon dioxide 
• 506-77-4 cyanogen chloride 
• 34698-60-7 3,4-dichloro-1,2,5-oxadiazole-N-oxide 

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