Dimethyl Phosphate Synthesis Essay

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  • Names
    IUPAC name

    Phosphorus trichloride

    Other names

    Phosphorus(III) chloride
    Phosphorous chloride

    Identifiers

    CAS Number

    3D model (JSmol)

    ChEBI
    ChemSpider
    ECHA InfoCard100.028.864
    EC Number231-749-3

    PubChemCID

    RTECS numberTH3675000
    UNII
    UN number1809

    InChI

    • InChI=1S/Cl3P/c1-4(2)3 Y
      Key: FAIAAWCVCHQXDN-UHFFFAOYSA-N Y
    Properties

    Chemical formula

    PCl3
    Molar mass137.33 g/mol
    AppearanceColorless to yellow fuming liquid[1]
    Odorlike hydrochloric acid[1]
    Density1.574 g/cm3
    Melting point−93.6 °C (−136.5 °F; 179.6 K)
    Boiling point76.1 °C (169.0 °F; 349.2 K)

    Solubility in water

    hydrolysis
    Solubility in other solventssoluble[vague] in benzene, CS2, ether, chloroform, CCl4, halogenated organic solvents
    reacts with ethanol
    Vapor pressure13.3 kPa

    Magnetic susceptibility (χ)

    −63.4·10−6 cm3/mol

    Refractive index (nD)

    1.5122 (21 °C)
    Viscosity0.65 cP (0 °C)
    0.438 cP (50 °C)

    Dipole moment

    0.97 D
    Thermochemistry

    Std enthalpy of
    formation (ΔfH298)

    −319.7 kJ/mol
    Hazards
    Safety data sheetSee: data page
    ICSC 0696

    EU classification (DSD) (outdated)

    T+XnC
    R-phrases(outdated)R14-R26/28-R35-R48/20
    S-phrases(outdated)(S1/2)-S7/8-S26-S36/37/39-S45
    NFPA 704
    Lethal dose or concentration (LD, LC):

    LD50 (median dose)

    18 mg/kg (rat, oral)[2]

    LC50 (median concentration)

    104 ppm (rat, 4 hr)
    50 ppm (guinea pig, 4 hr)[2]
    US health exposure limits (NIOSH):

    PEL (Permissible)

    TWA 0.5 ppm (3 mg/m3)[1]

    REL (Recommended)

    TWA 0.2 ppm (1.5 mg/m3) ST 0.5 ppm (3 mg/m3)[1]

    IDLH (Immediate danger)

    25 ppm[1]
    Related compounds

    Related phosphorus chlorides

    Phosphorus pentachloride
    Phosphorus oxychloride
    Diphosphorus tetrachloride

    Related compounds

    Phosphorus trifluoride
    Phosphorus tribromide
    Phosphorus triiodide
    Supplementary data page

    Structure and
    properties

    Refractive index (n),
    Dielectric constant (εr), etc.

    Thermodynamic
    data

    Phase behaviour
    solid–liquid–gas

    Spectral data

    UV, IR, NMR, MS

    Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

    N verify (what is YN ?)
    Infobox references

    Phosphorus trichloride is a chemical compound of phosphorus and chlorine, having the chemical formula PCl3. It has a trigonal pyramidal shape. It is the most important of the three phosphorus chlorides. It is an important industrial chemical, being used for the manufacture of organophosphorus compounds for a wide variety of applications. It has a 31P NMR signal at around +220 ppm with reference to a phosphoric acid standard.

    Chemical properties[edit]

    The phosphorus in PCl3 is often considered to have the +3 oxidation state and the chlorine atoms are considered to be in the −1 oxidation state. Most of its reactivity is consistent with this description.

    Redox reactions[edit]

    PCl3 is a precursor to other phosphorus compounds, undergoing oxidation to phosphorus pentachloride (PCl5), thiophosphoryl chloride (PSCl3), or phosphorus oxychloride (POCl3).

    If an electric discharge is passed through a mixture of PCl3 vapour and hydrogen gas, a rare chloride of phosphorus is formed, diphosphorus tetrachloride (P2Cl4).

    PCl3 as an electrophile[edit]

    Phosphorus trichloride is the precursor to organophosphorus compounds that contain one or more P(III) atoms, most notably phosphites and phosphonates. These compounds do not usually contain the chlorine atoms found in PCl3.

    PCl3 reacts vigorously with water to form phosphorous acid, H3PO3 and HCl:

    PCl3 + 3 H2O → H3PO3 + 3 HCl

    A large number of similar substitution reactions are known, the most important of which is the formation of phosphites by reaction with alcohols or phenols. For example, with phenol, triphenyl phosphite is formed:

    3 PhOH + PCl3 → P(OPh)3 + 3 HCl

    where "Ph" stands for phenyl group, -C6H5. Alcohols such as ethanol react similarly in the presence of a base such as a tertiary amine:[3]

    PCl3 + 3 EtOH + 3 R3N → P(OEt)3 + 3 R3NH+Cl

    In the absence of base, however, the reaction proceeds with the following stoichiometry to give diethylphosphite:[4][5]

    PCl3 + 3 EtOH → (EtO)2P(O)H + 2 HCl + EtCl

    Secondary amines (R2NH) form aminophosphines, e.g., tris(dimethylamino)phosphine. Thiols (RSH) form P(SR)3. An industrially relevant reaction of PCl3 with amines is phosphonomethylation, which employs formaldehyde:

    R2NH + PCl3 + CH2O → (HO)2P(O)CH2NR2 + 3 HCl

    Aminophosphonates are widely used as sequestring and antiscale agents in water treatment. The large volume herbicide glyphosate is also produced this way. The reaction of PCl3 with Grignard reagents and organolithium reagents is a useful method for the preparation of organic phosphines with the formula R3P (sometimes called phosphanes) such as triphenylphosphine, Ph3P.

    3 PhMgBr + PCl3 → Ph3P + 3 MgBrCl

    Under controlled conditions or especially with bulky organic groups, similar reactions afford less substituted derivatives such as chlorodiisopropylphosphine.

    PCl3 as a nucleophile[edit]

    Phosphorus trichloride has a lone pair, and therefore can act as a Lewis base, for example with the Lewis acids BBr3[6] it forms a 1:1 adduct, Br3B+PCl3. Metal complexes such as Ni(PCl3)4 are known. This Lewis basicity is exploited in one useful route to organophosphorus compounds using an alkyl chloride and aluminium chloride:

    PCl3 + RCl + AlCl3 → RPCl+
    3 + AlCl
    4

    The RPCl+
    3 product can then be decomposed with water to produce an alkylphosphonic dichloride RP(=O)Cl2.

    Preparation[edit]

    World production exceeds one-third of a million tonnes.[7] Phosphorus trichloride is prepared industrially by the reaction of chlorine with a refluxing solution of white phosphorus in phosphorus trichloride, with continuous removal of PCl3 as it is formed (in order to avoid the formation of PCl5).

    P4 + 6 Cl2 → 4 PCl3

    Industrial production of phosphorus trichloride is controlled under the Chemical Weapons Convention, where it is listed in schedule 3. In the laboratory it may be more convenient to use the less toxic red phosphorus.[8] It is sufficiently inexpensive that it would not be synthesized for laboratory use.

    Uses[edit]

    PCl3 is important indirectly as a precursor to PCl5, POCl3 and PSCl3, which are used in many applications, including herbicides, insecticides, plasticisers, oil additives, and flame retardants.

    For example, oxidation of PCl3 gives POCl3, which is used for the manufacture of triphenyl phosphate and tricresyl phosphate, which find application as flame retardants and plasticisers for PVC. They are also used to make insecticides such as diazinon. Phosphonates include the herbicideglyphosate.

    PCl3 is the precursor to triphenylphosphine for the Wittig reaction, and phosphite esters which may be used as industrial intermediates, or used in the Horner-Wadsworth-Emmons reaction, both important methods for making alkenes. It can be used to make trioctylphosphine oxide (TOPO), used as an extraction agent, although TOPO is usually made via the corresponding phosphine.

    PCl3 is also used directly as a reagent in organic synthesis. It is used to convert primary and secondary alcohols into alkyl chlorides, or carboxylic acids into acyl chlorides, although thionyl chloride generally gives better yields than PCl3.[9]

    Precautions[edit]

    PCl3 is toxic, with a concentration of 600 ppm being lethal in just a few minutes.[10] PCl3 is classified as very toxic and corrosive under EUDirective 67/548/EEC, and the risk phrases R14, R26/28, R35 and R48/20 are obligatory.

    Government agencies in the United States have set occupational exposure limits for PCl3. The Occupational Safety and Health Administration has set a permissible exposure limit at 0.5 ppm over a time-weighted average of 8 hours, while the National Institute for Occupational Safety and Health has set a recommended exposure limit at 0.2 ppm over a time-weighted average of 8 hours.[11] Additionally, PCl3 has been designated IDLH with a maximum exposure limit at 25 ppm.[12]

    History[edit]

    Phosphorus trichloride was first prepared in 1808 by the French chemists Joseph Louis Gay-Lussac and Louis Jacques Thénard by heating calomel (Hg2Cl2) with phosphorus.[13] Later during the same year, the English chemist Humphry Davy produced phosphorus trichloride by burning phosphorus in chlorine gas.[14]

    References[edit]

    1. ^ abcde"NIOSH Pocket Guide to Chemical Hazards #0511". National Institute for Occupational Safety and Health (NIOSH). 
    2. ^ ab"Phosphorus trichloride". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH). 
    3. ^A. H. Ford-Moore and B. J. Perry (1963). "Triethyl Phosphite". Organic Syntheses. ; Collective Volume, 4, p. 955 
    4. ^Malowan, John E. (1953). "Diethyl phosphite". Inorganic Syntheses. 4: 58–60. doi:10.1002/9780470132357.ch19. 
    5. ^Pedrosa, Leandro (2011). "Esterification of Phosphorus Trichloride with Alcohols; Diisopropyl phosphonate". ChemSpider Synthetic Pages. Royal Society of Chemistry: 488. doi:10.1039/SP488. 
    6. ^R. R. Holmes (1960). "An examination of the basic nature of the trihalides of phosphorus, arsenic and antimony,". Journal of Inorganic and Nuclear Chemistry. 12 (3-4): 266–275. doi:10.1016/0022-1902(60)80372-7. 
    7. ^Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9. 
    8. ^M. C. Forbes; C. A. Roswell; R. N. Maxson (1946). "Phosphorus(III) Chloride". Inorg. Synth.2: 145–7. doi:10.1002/9780470132333.ch42. 
    9. ^L. G. Wade, Jr. (2005). Organic Chemistry (6th ed.). Upper Saddle River, New Jersey, USA: Pearson/Prentice Hall. p. 477. 
    10. ^A. D. F. Toy (1973). The Chemistry of Phosphorus. Oxford, UK: Pergamon Press. 
    11. ^CDC - NIOSH Pocket Guide to Chemical Hazards
    12. ^Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs)
    13. ^Gay-Lussac; Thénard (27 May 1808). "Extrait de plusieurs notes sur les métaux de la potasse et de la soude, lues à l'Institut depuis le 12 janvier jusqu'au 16 mai" [Extracts from several notes on the metals potassium and sodium, read at the Institute from the 12th of January to the 16th of May]. Gazette Nationale, ou le Moniteur Universel (in French). 40 (148): 581–582.  From p. 582: "Seulement ils ont rapporté qu'en traitant le mercure doux par le phosphure, dans l'espérance d'avoir de l'acide muriatique bien sec, il ont trouvé une liqueur nouvelle très limpide, sans couleur, répandant de fortes vapeurs, s'enflammant spontanément lorsqu'on en imbibe le papier joseph; laquelle ne paraît être qu'une combinaison de phosphore, d'oxigène et d'acide muriatique, et par conséquent analogue à cette qu'on obtient en traitant le soufre par le gas acide muriatique oxigèné." (Only they reported that by treating calomel with phosphorus, in the hope of obtaining very dry hydrogen chloride, they found a new, very clear liquid, colorless, giving off strong vapors, spontaneously igniting when one soaks filter paper in it; which seems to be only a compound of phosphorus, oxygen, and hydrochloric acid, and thus analogous to what one obtains by treating sulfur with chlorine gas.)
    14. ^Davy, Humphry (1809). "The Bakerian Lecture. An account of some new analytical researches on the nature of certain bodies, particularly the alkalies, phosphorus, sulphur, carbonaceous matter, and the acids hitherto undecomposed; with some general observations on chemical theory". Philosophical Transactions of the Royal Society of London. 99: 39–104.  On pp. 94–95, Davy mentioned that when he burned phosphorus in chlorine gas ("oxymuriatic acid gas"), he obtained a clear liquid (phosphorus trichloride) and a white solid (phosphorus pentachloride).

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