102-85-2

Basic information

• Product Name: TRIBUTYL PHOSPHITE
• Synonyms: Tributyl phosphite 90%, technical grade;1,1’,1’’-phosphinidynetri-1-butano;Butyl phosphite ((C4H9O)3P);jp304;Phosphorus derivative;phosphorustributoxide(p(obu)3);Syn-O-Ad P-312;Tributoxyphosphine
• CAS NO: 102-85-2
• Molecular Formula: C₁₂H₂₇O₃P
• Molecular Weight: 250.31
• EINECS: 203-061-3
• Product Categories: Organic Building Blocks;Organic Phosphates/Phosphites;Phosphorus Compounds;organophosphorus compound
• Mol File: 102-85-2.mol
• Article Data: 11

Chemical Properties

• Melting Point: -80 °C
• Boiling Point: 125 °C
• Flash Point: 197 °F
• Appearance: colorless/liquid
• Density: 0.925 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.013mmHg at 25°C
• Refractive Index: n20/D 1.431(lit.)
• Water Solubility: Not miscible or difficult to mix in water.
• Sensitive: Air & Moisture Sensitive
• BRN: 1703866
• CAS DataBase Reference: TRIBUTYL PHOSPHITE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIBUTYL PHOSPHITE(102-85-2)
• EPA Substance Registry System: TRIBUTYL PHOSPHITE(102-85-2)

Safety Data

• Hazard Codes: C
• Statements: 21-34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3265 8/PG 3
• WGK Germany: 3
• RTECS: TH0875000
• TSCA: Yes
• Hazardous Substances Data: 102-85-2(Hazardous Substances Data)

Usage

Chemical Properties

Clear colorless liquid

Uses

Different sources of media describe the Uses of 102-85-2 differently. You can refer to the following data:
1. Tributyl phosphite may be employed as model lubricant additive and its surface chemistry on Fe3O4 in ultrahigh vacuum is investigated.
2. Tributyl Phosphite inhibits fluoroacetanilide poisoning in mammals.

General Description

Tributyl phosphite is an alkylphosphite and is reported to inhibit carboxylesterase activity.

Purification Methods

Fractionate the phosphite with an efficient column. It is stable in air but is slowly hydrolysed by H2O. [Gerrard J Chem Soc 1464 1940, Fertig et al. J Chem Soc 1488 1957, Fields J Am Chem Soc 80 2358 1958, Gillis et al. J Am Chem Soc 80 2999 1958, Beilstein 1 IV 1527.]

InChI:InChI=1/C12H27O3P/c1-4-7-10-13-16(14-11-8-5-2)15-12-9-6-3/h4-12H2,1-3H3

Synthetic route

O,O-dibutyl (tributoxymethyl)phosphonate → tri-n-butyl phosphite (102-85-2) + Dibutyl carbonate (542-52-9)

Conditions	Yield
With boron trifluoride diethyl etherate under 8 Torr; Heating;	A 71% B n/a

O,O-dibutyl (tributoxymethyl)phosphonate → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
With boron trifluoride diethyl etherate under 8 Torr; Heating;	71%

butan-1-ol (71-36-3) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
With potassium phosphate; tetrahexylammonium chloride; phosphorus trichloride In dichloromethane at 20℃; for 3h;	69%
With sodium hexachloroplatinate; phosphan at 24.9℃; Rate constant; Kinetics; also in the presence of LiCl, HCl, H2O, LiBr, NaI; var. conc. of reactants;
With ammonia; Petroleum ether; phosphorus trichloride

diethyl ester of 2-phenylethynylphosphonous acid (51104-80-4) + butan-1-ol (71-36-3) → tri-n-butyl phosphite (102-85-2) + phenylacetylene (536-74-3)

Conditions	Yield
With C4H9ONa Product distribution; Heating; oth. alcohols;	A 63% B n/a

S,S-diethyl-N-diethylamidodithiophosphite (42964-63-6) + butan-1-ol (71-36-3) → triethyl trithiophosphite (688-62-0) + tri-n-butyl phosphite (102-85-2)

Conditions	Yield
at 160℃; for 8h; Product distribution; Mechanism;	A 36% B 40%

S,S-diethyl-N-diethylamidodithiophosphite (42964-63-6) + butan-1-ol (71-36-3) → triethyl trithiophosphite (688-62-0) + tri-n-butyl phosphite (102-85-2) + diethylamine (109-89-7) + ethanethiol (75-08-1)

Conditions	Yield
at 160℃; for 8h;	A 36% B 40% C n/a D n/a

pyridine (110-86-1) + butyl dichlorophosphite (10496-13-6) + butan-1-ol (71-36-3) → tri-n-butyl phosphite (102-85-2)

triphenyl phosphite (101-02-0) + sodium butanolate (2372-45-4) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
With benzene

butyl dichlorophosphite (10496-13-6) + sodium butanolate (2372-45-4) → dibutyl chlorophosphite (4124-92-9) + tri-n-butyl phosphite (102-85-2)

sodium butanolate (2372-45-4) → dibutyl hydrogen phosphite (1809-19-4) + tri-n-butyl phosphite (102-85-2)

Conditions	Yield
With diethyl ether; phosphorus trichloride

dibutyl phosphonite (30653-71-5) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
boron trifluoride diethyl etherate at 100 - 160℃; decomposition;

dibutyl hydrogen phosphite (109-47-7) → tri-n-butyl phosphite (102-85-2) + diphosphorous acid tetrabutyl ester (54305-86-1) + n-butyl pyrophosphate (1474-75-5) + O,O'-dibutyl-phosphoric O,O'-dibutyl-phosphorous anhydride (682-23-5)

Conditions	Yield
With sodium perchlorate In acetonitrile electrochemical oxidation, 2.4 A h; Pt anode, Ni cathode; Ag/AgNO3 reference electrode; Title compound not separated from byproducts;

pyridine (110-86-1) + diethyl ether (60-29-7) + butan-1-ol (71-36-3) + phosphorus trichloride (7719-12-2, 52843-90-0) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
at -10℃;

magnesium butylate → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
With diethyl ether; phosphorus trichloride

diphosphorous acid tetrabutyl ester (54305-86-1) → tri-n-butyl phosphite (102-85-2) + nitryl chloride

Conditions	Yield
Multi-step reaction with 2 steps 1: 64 percent / BF3*Et2O / diethyl ether / Ambient temperature 2: 71 percent / fluoroboron etherate / 8 Torr / Heating View Scheme

dibutyl hydrogen phosphite (109-47-7) → tri-n-butyl phosphite (102-85-2) + nitryl chloride

Conditions	Yield
Multi-step reaction with 2 steps 1: 68 percent / sodium / diethyl ether / 0.5 h / 0 °C 2: 71 percent / fluoroboron etherate / 8 Torr / Heating View Scheme

trans-(ruthenium(II)dimethylglyoximate)2(triphenylphosphine)(tri-n-butylphosphite) + triphenylphosphine (603-35-0) → trans-(ruthenium(II)dimethylglyoximate)2(triphenylphosphine)2 + tri-n-butyl phosphite (102-85-2)

Conditions	Yield
In toluene Kinetics; Soln. is prepared by injecting the ligand into serum-capped cell (under N2) containing the thermostated soln. of the complex.; UV-spectroscopy.;

dibutyl hydrogen phosphite (1809-19-4) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium 2: boron trifluoride diethyl etherate / 8 Torr / Heating View Scheme

diphosphorous acid tetrabutyl ester (54305-86-1) → tri-n-butyl phosphite (102-85-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: boron trifluoride diethyl etherate / diethyl ether / 20 °C 2: boron trifluoride diethyl etherate / 8 Torr / Heating View Scheme

1,4-dibromo-butane (110-52-1) + tri-n-butyl phosphite (102-85-2) → dibutyl(4-bromobutyl)phosphonate

Conditions	Yield
at 118℃; for 6h;	100%

tri-n-butyl phosphite (102-85-2) + 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (21988-87-4) → C36H69O9P3 (612040-41-2)

Conditions	Yield
at 130℃; for 16.5h;	100%

tricarbonyl(η-tropylium)chromium tetrafluoroborate + tri-n-butyl phosphite (102-85-2) → tricarbonyl[1-6-η-7-tri(nbutoxy)phosphoniocyclohepta-1,3,5-triene] chromium tetrafluoroborate (61824-16-6)

Conditions	Yield
In dichloromethane org. compd. addn. dropwise to Cr-compd. suspn., pptn. on slow diethyl ether addn.; ppt. filtration off, washing (diethyl ether); elem. anal.;	100%
In acetone Kinetics; excess org. compd. addn. to Cr-compd. soln. at const. temp. (1, 5, 10, 15 and 20.5°C); stopped-flow UV spectroscopic monitoring;

tri-n-butyl phosphite (102-85-2) + 2,3,4,5,6-pentabromobenzyl bromide (38521-51-6) → dibutyl pentabromobenzylphosphonate (95452-28-1)

Conditions	Yield
at 25 - 156℃; Inert atmosphere;	100%

1-iodo-butane (542-69-8) + tri-n-butyl phosphite (102-85-2) → dibutyl butylphosphonate (78-46-6)

Conditions	Yield
at 160℃; for 1.5h; Michaelis-Arbuzov Synthesis;	99%
at 150 - 160℃;

tri-n-butyl phosphite (102-85-2) + toluene-4-sulfonic acid (104-15-4) → dibutyl hydrogen phosphite (1809-19-4)

Conditions	Yield
In 1,2-dichloro-ethane for 24h; Ambient temperature; molar ratio 1:1;	98%

C21H21F3INO + tri-n-butyl phosphite (102-85-2) → 9-[5-(dibutoxyphosphinyl)pentyl]-N-(2,2,2-trifluoroethyl)-9H-fluorene-9-carboxamide

Conditions	Yield
at 120℃; for 18h; Neat (no solvent);	98%

C22H23F3INO + tri-n-butyl phosphite (102-85-2) → [6-[9-[((2,2,2-trifluoroethyl)amino)carbonyl]-9H-fluoren-9-yl]hexyl]phosphonic acid, dibutyl ester

Conditions	Yield
at 120℃; for 18h; Neat (no solvent);	98%

tri-n-butyl phosphite (102-85-2) + octadecyl bromoacetate (18992-03-5) → octadecyl diethylphosphonoacetate (951643-33-7)

Conditions	Yield
at 100 - 150℃; Inert atmosphere;	98%

tri-n-butyl phosphite (102-85-2) + Cyclohepta-1,3,5-triene (544-25-2) → dibutyl cyclohepta-2,4,6-trien-1-ylphosphonate

Conditions	Yield
Stage #1: Cyclohepta-1,3,5-triene With 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 20℃; for 0.0833333h; Michaelis-Arbuzov Synthesis; Inert atmosphere; Stage #2: tri-n-butyl phosphite	98%

tri-n-butyl phosphite (102-85-2) + α,α'-dibromo-o-xylene (91-13-4) → tetrabutyl (1,2-phenylenebis(methylene))bis(phosphonate)

Conditions	Yield
at 120℃; for 16h;	97%
at 120℃; for 16h;	97%

tri-n-butyl phosphite (102-85-2) + Chlorodiisopropylphosphane (40244-90-4) → 1,1-dibutoxy-2,2-diisopropyldiphosphine 1-oxide (42003-70-3)

Conditions	Yield
With nickel dichloride at 150℃; for 0.5h;	96%

tri-n-butyl phosphite (102-85-2) → 9-[5-(dibutoxyphosphinyl)pentyl]-N-propyl-9H-fluorene-9-carboxamide

Conditions	Yield
at 120℃; for 18h;	96%

tri-n-butyl phosphite (102-85-2) + 1,3,5-Tris(bromomethyl)benzene (18226-42-1) → C33H63O9P3 (876908-95-1)

Conditions	Yield
at 130℃; for 16.5h;	96%

tri-n-butyl phosphite (102-85-2) + 1-azido-1-deoxy-β-D-glucopyranoside tetraacetate (13992-25-1) → 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl dibutyl phosphoramidate (1240498-34-3)

Conditions	Yield
In dichloromethane at 20℃; Staudinger reaction; stereoselective reaction;	96%
In tetrahydrofuran at 25℃; for 24h; Staudinger Azide Reduction; chemoselective reaction;	90%

tri-n-butyl phosphite (102-85-2) + 3,5-di-tert-butyl-2-hydroxybenzaldehyde (37942-07-7) + malononitrile (109-77-3) → dibutyl (2-amino-6,8-di-tert-butyl-3-cyano-4H-chromen-4-yl)phosphonate

Conditions	Yield
With silver In ethanol for 0.5h; Reflux;	96%

trimethyl phosphite (512-56-1) + 1,1,1-tri(hydroxymethyl)propane (77-99-6) + tri-n-butyl phosphite (102-85-2) + Dipentaerythritol (126-58-9) → C13H25O10P3

Conditions	Yield
Stage #1: 1,1,1-tri(hydroxymethyl)propane; tri-n-butyl phosphite; Dipentaerythritol With sulfuric acid at 85℃; for 5h; Inert atmosphere; Stage #2: trimethyl phosphite With 1-Bromopentane at 185℃; for 16h;	95.6%

tri-n-butyl phosphite (102-85-2) + tert-butyldiiodophosphane (66517-44-0) → C20H45O6P3

Conditions	Yield
In dichloromethane at -40℃;	95%

tri-n-butyl phosphite (102-85-2) → dibutyl butylphosphonate (78-46-6)

Conditions	Yield
With iodine for 24h; Heating;	95%
With trifluorormethanesulfonic acid at 60℃; for 16h; Schlenk technique; Inert atmosphere;	85%
With trifluorormethanesulfonic acid at 60℃; for 16h; Inert atmosphere;

tri-n-butyl phosphite (102-85-2) + Hexafluoroacetone (684-16-2) → 2,2,2-Tributoxy-4,4,5,5-tetrakis-trifluoromethyl-2λ5-[1,3,2]dioxaphospholane (87779-54-2)

Conditions	Yield
at 25℃; for 96h; sealed tube;	95%

tri-n-butyl phosphite (102-85-2) + E-3-bromo-1-propenyl t-butyl sulfone (300344-95-0) → [(E)-3-(2-Methyl-propane-2-sulfonyl)-allyl]-phosphonic acid dibutyl ester (300344-96-1)

Conditions	Yield
at 130℃; for 12h; Arbusov substitution;	95%

(1,5-cylooctadiene)di-iodoplatinum(II) (12266-72-7) + tri-n-butyl phosphite (102-85-2) → cis-diiodobis(tri-n-butyl phosphite)platinum(II) (97277-53-7)

Conditions	Yield
In hexane (white spot N2); to the starting complex in hexane addn. of the phosphite (2,5 h); oil is dried under vac., chromy., elem. anal.;	95%

tri-n-butyl phosphite (102-85-2) + C110H55ClO10 → C114H64O10

Conditions	Yield
In toluene at 100 - 105℃; Arbuzov Reaction; Inert atmosphere;	95%

tri-n-butyl phosphite (102-85-2) + (4-chloro-benzylidene)-hydrazinecarboxylic acid ethyl ester (3206-35-7) + dimethyl acetylenedicarboxylate (762-42-5) → dimethyl 2-(dibutoxyphosphoryl)-3-[2-(4-chlorobenzylidene)-1-(ethoxycarbonyl)hydrazino]succinate

Conditions	Yield
In acetonitrile at 20℃; for 24h;	94%

tri-n-butyl phosphite (102-85-2) + Tosyl isocyanate (4083-64-1) + aniline (62-53-3) → C18H22N2O3S (1256338-86-9)

Conditions	Yield
Stage #1: Tosyl isocyanate; aniline In dichloromethane at 25℃; for 0.0833333h; Stage #2: tri-n-butyl phosphite With dimethyl acetylenedicarboxylate In dichloromethane at 25℃; for 2h;	94%

2-hydroxy-5-methoxybenzaldehyde (672-13-9) + tri-n-butyl phosphite (102-85-2) + malononitrile (109-77-3) → dibutyl (2-amino-3-cyano-6-methoxy-4H-chromen-4-yl)phosphonate

Conditions	Yield
With silver In ethanol for 0.25h; Reflux;	94%

tri-n-butyl phosphite (102-85-2) + Cholestanol (80-97-7) → Phosphoric acid dibutyl ester (3S,5S,8R,9S,10S,13R,14S,17R)-17-((R)-1,5-dimethyl-hexyl)-10,13-dimethyl-hexadecahydro-cyclopenta[a]phenanthren-3-yl ester

Conditions	Yield
With lutidine; tellurium tetrachloride In dichloromethane for 1h; Ambient temperature;	93%

tri-n-butyl phosphite (102-85-2) + 1-dodecylthiol (112-55-0) → Thiophosphoric acid O,O'-dibutyl ester S-dodecyl ester

Conditions	Yield
With 2,6-dimethylpyridine; tellurium tetrachloride In dichloromethane for 1h; -42 deg C, 5-10 min; room temp. 1 h;	93%

tri-n-butyl phosphite (102-85-2) + 4-bromo-trans-crotonic acid ethyl ester (37746-78-4) → (E)-4-(Dibutoxy-phosphoryl)-but-2-enoic acid ethyl ester

Conditions	Yield
at 85 - 90℃; for 12h;	93%

tri-n-butyl phosphite (102-85-2) + o-toluidine (95-53-4) + recorcinol (108-46-3) → 3-(o-tolylamino)phenol (6264-98-8)

Conditions	Yield
In water	93%

Upstream product

• 101-02-0 triphenyl phosphite 
• 2372-45-4 sodium butanolate 
• 54305-86-1 diphosphorous acid tetrabutyl ester 
• 1809-19-4 dibutyl hydrogen phosphite 
• 603-35-0 triphenylphosphine 
• 109-47-7 dibutyl hydrogen phosphite 
• 110-86-1 pyridine 
• 60-29-7 diethyl ether 
• 71-36-3 butan-1-ol 
• 7719-12-2 phosphorus trichloride 
• 51104-80-4 diethyl ester of 2-phenylethynylphosphonous acid 
• 42964-63-6 S,S-diethyl-N-diethylamidodithiophosphite 
• 30653-71-5 dibutyl phosphonite 
• 10496-13-6 butyl dichlorophosphite 

Downstream Products

• 57806-89-0 1-p-Dimethylaminophenyl-1-dibutoxyphosphinyl-norcaran 
• 603-35-0 triphenylphosphine 
• 82383-23-1 (OC)5CrC(C₆H₅)(OC₂H₅)P(O(CH₂)3CH₃)3 
• 7242-59-3 dibutyl methyl phosphate 
• 126-73-8 phosphoric acid tributyl ester 
• 78-47-7 O,O,O-tributyl phosphorothioate 
• 7264-96-2 di-n-butyl morpholinophosphonate 
• 96004-84-1 2,2'-Dinitro-α-butyloxy-α'-dibutyloxyphosphono-dibenzylaether 
• 2902-90-1 β-(O.O-Dibutyl-phosphono)-zimtsaeure-butylester 
• 35812-39-6 (2-Methoxy-ethyl)-phosphoramidic acid dibutyl ester 
• 1707-11-5 1,2-Bis-di-n-butylphosphono-1,2-diphenyl-aethan 
• 1034-94-2 dibutyl (2-oxo-2-phenylethyl)phosphonate 
• 70508-52-0 Dibutyl--o-hydroxyanilino-methylphosphonat 
• 4762-64-5 allyl phophonate de dibutyl 

Relevant articles and documents

Synthesis and reactivity of substituted α-carbonylphosphonites and their derivatives

Convenient methods for the synthesis of functionalized organophosphorus compounds containing carbonyl groups as well as di- or trialkoxymethyl fragments attached to phosphorus, and their derivatives, starting from the available derivatives of trivalent phosphorus acids, are proposed, and some properties of the new functionalized organophosphorus compounds are presented. So, the alkylation and acylation reaction of (dialkoxymethyl) phosphonites and their analogs have been studied. It is found that the Arbuzov rearrangement of these compounds was accompanied by the phosphorus-carbon bond cleavage with unique retention of the three-coordinate phosphorus.

Synthesis of tervalent phosphorus esters in biphasic system using potassium phosphate as unique solid base

The synthesis of tervalent phosphorus esters continues to be a significant area of interest, much of it again directed toward the synthesis of phosphite ligands for metal-catalyzed reactions. Typically, they were obtained through esterification of the corresponding phosphorus chlorides with the appropriate alcohols in the presence of an amine. In this paper, we present a new method for the synthesis of tervalent phosphorus esters, not yet mentioned in the literature, when potassium phosphate, as a unique base, is used in liquid-solid system. Symmetrical and unsymmetrical phosphites were obtained with good yields (65%-80%) using this method. The compounds were characterized by 31P NMR spectroscopy.

Electrochemical Oxidation of Metal Dialkyl Phosphites and Their Reaction with Halogens

Electrochemical oxidation of sodium dialkyl phosphites with alkyl radicals of normal structure leads to formation of tetraalkyl pyrophosphites as the main products, while electrochemical oxidation of litium dialkyl phosphites and sodium salts with branched alkyl radicals yields tetraalkyl hypophosphates. The reaction of metal dialkyl phosphites with halogens leads to analogous results.