866-23-9

Basic information

• Product Name: DIETHYL TRICHLOROMETHYLPHOSPHONATE
• Synonyms: trichloro-methanephosphonicacidiethylester;trichloromethyl-phosphonicacidiethylester;TIMTEC-BB SBB008195;DIETHYL TRICHLOROMETHYLPHOSPHONATE;DIETHYL (TRICHLOROMETHYL)PHOSPHONATE, 97 %;(Trichloromethyl)phosphonic acid diethyl;Ro-30658;Trichloromethylphosphonic acid diethyl
• CAS NO: 866-23-9
• Molecular Formula: C₅H₁₀Cl₃O₃P
• Molecular Weight: 255.46
• Product Categories: Phosphonates/Phosphinates;Organic Building Blocks;Phosphorus Compounds;Building Blocks;Chemical Synthesis;Organic Building Blocks;Phosphorus Compounds
• Mol File: 866-23-9.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 130-131 °C14 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: /Liquid
• Density: 1.362 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0204mmHg at 25°C
• Refractive Index: n20/D 1.463(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: 4.5g/L(25 oC)
• BRN: 1210640
• CAS DataBase Reference: DIETHYL TRICHLOROMETHYLPHOSPHONATE(CAS DataBase Reference)
• NIST Chemistry Reference: DIETHYL TRICHLOROMETHYLPHOSPHONATE(866-23-9)
• EPA Substance Registry System: DIETHYL TRICHLOROMETHYLPHOSPHONATE(866-23-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-22
• Safety Statements: 26-36-60-36/37
• RIDADR: UN3278
• WGK Germany: 3
• RTECS: TA0988000
• F: 9-21
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 866-23-9(Hazardous Substances Data)

Usage

Chemical Description

Diethyl trichloromethylphosphonate is an organophosphorus compound with the chemical formula (C2H5O)2P(O)CCl3.

Uses

Diethyl (trichloromethyl)phosphonate may be used in the synthesis of chlorovinyl phosphonates via reaction with aldehydes and ketones.

Preparation

Diethyl trichloromethylphosphonate was also obtained from diethyltrimethylsilyl phosphite in 60 % yield, and from benzyldiethyl phosphite in the presence of dibenzoyl peroxide and an ultraviolet source in a radical induced reaction in 87 % yield (compared to 26 % without the dibenzoyl peroxide).

Application

Diethyl trichloromethylphosphonate has been used as a carbenoid precursor in the reaction with Bu3B.Diethyl trichloromethylphosphonate is used mainly in the synthesis of 1,1-dichloro-1-alkenes from carbonyl compounds via Horner–Wadsworth–Emmons (HWE)-type reactions.Diethyl trichloromethylphosphonate reacts with olefins under Cu(I) or Fe(III) catalysis to give insertion of the olefinic substrate into one of the C–Cl bonds.

General Description

Addition reaction of diethyl (trichloromethyl)phosphonate to olefins by non-chain catalytic reactions catalyzed by copper amine complexes has been reported. Irradiation of diethyl (trichloromethyl)phosphonate in MeCN is reported to afford corresponding monoesters and olefins, via photochemical type II elimination reaction.

InChI:InChI=1/C5H10Cl3O3P/c1-3-10-12(9,11-4-2)5(6,7)8/h3-4H2,1-2H3

Upstream product

• 56-23-5 tetrachloromethane 
• 21646-99-1 diphosphorous acid tetraethyl ester 
• 77075-13-9 1-adamantyl diethyl phosphite 
• 13716-45-5 diethyl trimethylsilyl phosphite 
• 122-52-1 triethyl phosphite 
• 660-68-4 diethyl amine hydrochloride 
• 109-89-7 diethylamine 

Downstream Products

• 109-94-4 formic acid ethyl ester 
• 3167-62-2 diethyl (dichloromethyl)phosphonate 
• 38862-78-1 1,1-dichloro-3-phenylpropene 
• 74638-85-0 diethoxyphosphoryloxy-2-phenylethene 
• 105-37-3 Ethyl propionate 
• 97-62-1 Ethyl isobutyrate 
• 93-89-0 benzoic acid ethyl ester 
• 383-63-1 ethyl trifluoroacetate, 
• 41448-64-0 1-(2,2-dichlorovinyl)-4-methoxybenzene 
• 74-85-1 ethene 
• 44864-94-0 trichloromethyl-phosphonic acid monoethyl ester 
• 78-40-0 triethyl phosphate 
• 3167-63-3 diethyl chloromethylphosphonate 
• 64-18-6 formic acid 

Relevant articles and documents

DIREKTSYNTHESE VON N,N-DIORGANYL-PHOSPHORSAEUREDIALKYLESTERAMIDEN AUS TRIALKYLPHOSPHITEN

Dialkyl N,N-Diorganylphosphoroamidates result in the reaction of trialkylphosphites with secondary amines and tetrachlormethane if amine hydrochlorides are used as catalysts.A reaction mechanism is proposed.Key words: N,N-Diorganylphosphoroamidates; trialkylphosphites; tetrachlormethane.

REACTIVITY OF TRIETHYL PHOSPHITE WITH TETRACHLOROMETHANE : ELECTRON TRANSFER VERSUS IONIC SUBSTITUTION ON "POSITIVE" HALOGEN

The reaction of triethyl phosphite (1) with tetrachloromethane (2) has been studied from a mechanistic point of view. 1 reacts at 80 deg C with 2 to form diethyltrichloromethanephosphonate (3) (85-90percent yield) and chloroethane (4) (80percent yield).Several results hint at a radical chain mechanism (like SRN1).Trichloromethyl radical is trapped by 2,6-di-t-butyl-4-cresol (BHT), the reaction may be initiated with UV radiation (254 nm) and a charge transfer complex (CTC) is formed between 1 and 2 ; furthermore, the reaction is inhibited by 7,7',8,8' tetracyanoquinodimethane (TCNQ).Tris(cyclopropylmethyl)phosphite (12a) and tri(1-hexene-6-yl) phosphite (7a) are used as potential radical clocks in these reactions.The first leads inter alia to 3-chloro-1-butene (17) and the second to 5-chloro-1-hexene (11), the first therefore suggests a radical mechanism but not the second.However in this particular case even the results obtained with the tris(cyclopropylmethyl)phosphite may be rationalized also by an ionic mechanism.For the photostimulated reaction , the overall quantum yield is 0.1.The electrochemical oxidation of 1 with added CCl4 does not account for a radical chain process as the main pathway.Furthermore, the application of Marcus analysis to reaction viewed as an electron transfer leads to a calculated rate constant in the range of 10-20 M-1s-1.The synergy of the techniques that we used lead us to conclude that the thermal reaction is in fact an SNCl+ substitution.The radical intermediates would mainly be derived from the electron-transfer reaction between CCl3- and CCl4 the importance of which increases when special conditions such as hν activation are applied.Reaction therefore provides an example where the observed paramagnetic species during a D/A interaction could deceptively suggest an electron-transfer between D and A whereas they originate from an interaction between A and an electron donor formed after or during the first step of the reaction.

QUESTION OF THE OUTGOING GROUP IN THE ARBUZOV REACTION OF 1-ADAMANTYL DIETHYL PHOSPHITE

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