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{{chembox |
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{{Chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 409109463 |
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| ImageFile=tributylphosphine.png |
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| verifiedrevid = 447105996 |
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| ImageSize=150px |
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| ImageFile=tributylphosphine.png |
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| ImageFile1=Tributylphosphine-3D-vdW.png |
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| ImageSize=100px |
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| IUPACName=Tributylphosphane |
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| OtherNames=Tributylphosphine |
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| ImageFile1=Tributylphosphine-3D-vdW.png |
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| ImageSize1=120px |
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| Section1 = {{Chembox Identifiers |
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| ImageCaption1={{legend|orange|], P}}{{legend|rgb(64, 64, 64)|], C}}{{legend|white|], H}} |
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| CASNo_Ref = {{cascite}} |
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| PIN=Tributylphosphane |
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| OtherNames=Tributylphosphine |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo=998-40-3 |
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| CASNo=998-40-3 |
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| ChEMBL = 3185473 |
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| EINECS=213-651-2 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| SMILES=CCCCP(CCCC)CCCC |
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| UNII = 0O52FJR7WN |
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| DispInChI=1/C12H27P/c1-4-7-<br/>10-13(11-8-5-2)12-9-6<br/>-3/h4-12H2,1-3H3 |
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| UNNumber = 3254 |
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| InChI=1/C12H27P/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3}} |
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| PubChem = 13831 |
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| Section2={{Chembox Properties |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| C = 12 | H = 27 | P = 1 |
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| ChemSpiderID = 13231 |
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| Formula=C{{su|b=12}}H{{su|b=27}}P |
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| EINECS=213-651-2 |
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| MolarMass=204.25 g/mol |
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| SMILES=CCCCP(CCCC)CCCC |
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| Appearance=Colorless oily liquid |
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| InChI =1/C12H27P/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3 |
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| Density=0.82 g/ml |
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| InChIKey=TUQOTMZNTHZOKS-UHFFFAOYAQ |
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| Solubility=negligible |
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}} |
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| Solvent=Water |
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|Section2={{Chembox Properties |
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| MeltingPtK=213 |
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| Formula={{chem2|P(CH2CH2CH2CH3)3}} |
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| BoilingPtK=513 |
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| C=12|H=27|P=1 |
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| Boilink_notes=(150 °C @ 50 mmHg) |
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| Appearance=Colorless oily liquid |
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| Dipole=?}} |
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| Density=0.82 g/ml |
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| Section3={{Chembox Hazards |
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| Odor=Stench, nauseating |
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| Solubility=negligible |
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| Solvent= |
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| SolubleOther = organic solvents such as ] |
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| MeltingPtK=213 |
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| BoilingPtK=513 |
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| BoilingPt_notes =({{convert|150|C|F K}} at 50 mmHg) |
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| Dipole= |
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}} |
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|Section7={{Chembox Hazards |
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| NFPA-H = 1 |
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| NFPA-H = 1 |
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| NFPA-F = 3 |
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| NFPA-F = 3 |
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| NFPA-R = 2 |
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| NFPA-R = 2 |
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| GHSPictograms = {{GHS flame}}{{GHS corrosion}}{{GHS exclamation mark}}{{GHS environment}} |
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| NFPA-O = |
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| GHSSignalWord = Danger |
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| RPhrases = {{R17}} {{R21}} {{R22}} {{R34}} {{R38}} |
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| HPhrases = {{H-phrases|226|250|251|302|312|314|411}} |
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| MainHazards=Stench, Flammable, Corrosive |
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| PPhrases = {{P-phrases|210|222|233|235+410|240|241|242|243|260|264|270|273|280|301+312|301+330+331|302+334|302+352|303+361+353|304+340|305+351+338|310|312|321|322|330|363|370+378|391|403+235|405|407|413|420|422|501}} |
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| FlashPt=117 °C |
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| MainHazards=Stench, Flammable, Corrosive |
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| Autoignition=168 °C}} |
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| LD50 = 750 mg/kg (oral, rats) |
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| Section4={{Chembox Supplement}} |
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| FlashPtC = 117 |
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| Section5={{Chembox Related |
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| AutoignitionPtC = 168 |
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| OtherFunctn=]<br/>] |
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}} |
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| Function=Tertiary phosphine}} |
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|Section5={{Chembox Related |
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| OtherFunction={{ubl|]|]|]}} |
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'''Tributylphosphine''',<ref>'''Tributylphosphine''' is the most widely used name for this compound. However ] prefers the name '''tributylphosphane''', which is also the U.S. proper shipping name (49 CFR 172.101).</ref> ] P(C{{su|b=4}}H{{su|b=9}}){{su|b=3}} or PBu{{su|b=3}}, is a ], most commonly encountered as a ] in ] ]es. It is an oily liquid at room temperature, with a nauseating odor. It reacts slowly with atmospheric ], and rapidly with other ]s, to give the corresponding ]. It is usually handled using ]s. |
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'''Tributylphosphine''' is the ] with the ] {{chem2|P(CH2CH2CH2CH3)3}}, often abbreviated as {{chem2|P]3}}. It is a ]. It is an oily liquid at room temperature, with a nauseating odor. It reacts slowly with atmospheric ], and rapidly with other ]s, to give tributylphosphine oxide. It is usually handled using ]s. |
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== Preparation == |
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==Preparation== |
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Tributylphosphine is prepared industrially by the addition of ] to ]: the addition proceeds by a ] mechanism, and so the ] is not followed. |
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Tributylphosphine is prepared industrially by the ] of ] with ]: the addition proceeds by a ] mechanism, and so the ] is not followed.<ref>{{cite journal |title=Phosphine in the synthesis of organophosphorus compounds |last1=Trofimov |first1=Boris A. |last2=Arbuzova |first2=Svetlana N. |last3=Gusarova |first3=Nina K. |year=1999 |journal=Russian Chemical Reviews |volume=68 |issue=3 |pages=215–227 |doi=10.1070/RC1999v068n03ABEH000464 |bibcode=1999RuCRv..68..215T |s2cid=250775640}}</ref> |
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:{{chem2|PH3 + 3 CH2\dCHCH2CH3 → P(CH2CH2CH2CH3)3}} |
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::PH{{su|b=3}} + 3CH{{su|b=2}}=CHCH{{su|b=2}}CH{{su|b=3}} → P(CH{{su|b=2}}CH{{su|b=2}}CH{{su|b=2}}CH{{su|b=3}}){{su|b=3}} |
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Tributylphosphine can be prepared in the laboratory by reaction of the appropriate ] with ] although, as it is commercially available at reasonable prices, it is rare to have to perform the small-scale preparation. |
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Tributylphosphine can be prepared in the laboratory by reaction of the appropriate ] with ] although, as it is commercially available at reasonable prices, it is rare to have to perform the small-scale preparation. |
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:{{chem2|3 CH3CH2CH2CH2MgCl + PCl3 → P(CH2CH2CH2CH3)3 + 3 MgCl2}} |
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::3BuMgCl + PCl{{su|b=3}} → PBu{{su|b=3}} + 3MgCl{{su|b=2}} |
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== Use == |
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==Reactions== |
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Tributylphosphine reacts with ] to give the corresponding ] (here tributylphosphine oxide): |
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Tributylphosphine finds some industrial use as a ] in the ]-catalyzed ] of ]s, where it greatly increases the ratio of straight-chain ]s to branched-chain aldehydes in the product mixture.<ref>{{cite journal | last = Bell | first = P. | coauthors = Rupilus, W.; & Asinger, F. | year = 1968 | title = Zur Frage der Isomerenbildung bei der Hydroformylierung Höhermolekularer Olefine mit Komplexen Kobalt- und Rhodiumkatalysatoren | journal = ] | pages = 3262–66}}</ref> However, ] is even more effective for this purpose (although more expensive) and, in any case, rhodium catalysts are usually preferred to cobalt catalysts for the hydroformylation of alkenes. |
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:{{chem2|2 P(CH2CH2CH2CH3)3 + O2 → 2 O\dP(CH2CH2CH2CH3)3}} |
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Because this reaction is so fast, the compound is usually handled under an ]. |
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The phosphine is also easily ]. For example, ] gives a ] (here tributyl(phenylmethyl)phosphonium chloride):<ref name=Ullmann>Jürgen Svara, Norbert Weferling and Thomas Hofmann "Phosphorus Compounds, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, 2006, Wiley-VCH, Weinheim. {{doi|10.1002/14356007.a19_545.pub2}}</ref> |
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Tributylphosphine is also a common ] for the preparation of ]es of ]s in relatively low ]s, as it is cheap and less ]. It has a conveniently low volatility, which makes it easier to handle than other trialkylphosphines. Although its complexes are generally highly soluble, they are often more difficult to crystallize compared to complexes of more rigid phosphines. Furthermore, the 1H NMR properties are less easily interpreted and can mask signals for other ligands. Compared to other ]s, it is compact (]: 136°) and basic (]: 5.25 cm<sup>–1</sup>)<ref>{{cite journal | last = Rahman | first = M. M. | coauthors = Liu, H. Y.; Prock, A.; & Giering, W. P. | year = 1987 | title = Steric and Electronic Factors influencing Transition-Metal–Phosphorus(III) Bonding | journal = ] | volume = 6 | issue = 3 | pages = 650–58 | doi = 10.1021/om00146a037}}</ref> |
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:{{chem2|P(CH2CH2CH2CH3)3 + ]CH2Cl → +Cl−}} |
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Tributylphosphine is a common ] for the preparation of ] of ]s in low ]s. It is cheaper and less ] than ] and other ]. Although its complexes are generally highly ], they are often more difficult to ] compared to complexes of more rigid phosphines. Furthermore, the ] properties are less easily interpreted and can mask signals for other ligands. Compared to other ]s, it is compact (]: 136°) and basic (]: 5.25 cm<sup>−1</sup>)<ref>{{cite journal |last=Rahman |first=M. M. |author2=Liu, H. Y. |author3=Prock, A. |author4=Giering, W. P. |year=1987 |title=Steric and Electronic Factors influencing Transition-Metal–Phosphorus(III) Bonding |journal=] |volume=6 |issue=3 |pages=650–58 |doi=10.1021/om00146a037}}</ref> |
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== Hazards == |
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The main laboratory inconvenience of tributylphosphine is its extremely strong and unpleasant smell. All manipulations must be carried out in an efficient ], and glassware which has come into contact with the compound must be decontaminated before leaving the hood. Because tributylphosphine must be protected from the atmosphere, it is usually handled using syringe techniques. The manipulation of large quantities requires specific precautions to prevent the release of the vapour into the environment. For transport purposes, it is classified as a "spontaneously flammable liquid" (group 4.2), although this is rarely a significant problem in the laboratory use of small quantities: it may not be transported by air.<ref>49 ] 172.101.</ref> |
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== References == |
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==Use== |
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Tributylphosphine finds some industrial use as a ] in the ]-catalyzed ] of ]s, where it greatly increases the ratio of ] ]s to ] aldehydes in the product mixture.<ref>{{cite journal |last=Bell |first=P. |author2=Rupilus, W. |author3=Asinger, F. |year=1968 |title=Zur Frage der Isomerenbildung bei der Hydroformylierung Höhermolekularer Olefine mit Komplexen Kobalt- und Rhodiumkatalysatoren |journal=] |pages=3261–66 |volume=9 |issue=29 |doi=10.1016/S0040-4039(00)89542-8}}</ref> However, ] is even more effective for this purpose (although more expensive) and, in any case, ] ]s are usually preferred to ] catalysts for the hydroformylation of alkenes. |
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<references /> |
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It is the precursor to the ] (2,4-dichlorobenzyl)tributylphosphonium chloride ("]").<ref name=Ullmann/> |
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== External links == |
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Although tributylphosphine is generally regarded as toxic, its biological effects can be manipulated by ] strategies. For example, a ] version of tributylphosphine has been used to induce ] ] and ] in ]s.<ref>{{cite journal |last1=Tirla |first1=A. |last2=Rivera-Fuentes |first2=P. |title=Development of a Photoactivatable Phosphine Probe for Induction of Intracellular Reductive Stress with Single-Cell Precision |journal=Angew. Chem. Int. Ed. |date=2016 |volume=55 |issue=47 |pages=14709–14712 |doi=10.1002/anie.201608779 |pmid=27763731 |hdl=20.500.11850/123593 |hdl-access=free}}</ref> |
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<!-- Metadata: see ] --> |
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{{InChI |
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==Odor== |
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|InChI=1/C12H27P/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3 |
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The main laboratory inconvenience of tributylphosphine is its unpleasant smell. |
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|InChIKey=TUQOTMZNTHZOKS-UHFFFAOYAQ |
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|CASRN=998-40-3 |
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==Hazards== |
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|PIN=Tributylphosphane |
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Tributylphosphine is moderately toxic, with an ] of 750 mg/kg (oral, rats).<ref name=Ullmann/> |
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==References== |
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{{Reflist}} |
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==External links== |
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