682-09-7

Basic information

• Product Name: Trimethylolpropane diallyl ether
• Synonyms: 1,1,1-TRIMETHYLOLPROPANE DIALLYL ETHER;1,1,1-(TRIHYDROXYMETHYL)PROPANE DIALLYL ETHER;2-ETHYL-2-(HYDROXYMETHYL)-1 3-PROPANEDIOL DIALLYL ETHER;2,2-BIS(ALLYLOXYMETHYL)-1-BUTANOL;TRIMETHYLOLPROPANE DIALLYL ETHER;1-Butanol,2,2-bis[(2-propenyloxy)methyl]-;2,2-bis[(2-propenyloxy)methyl]-1-butano;2,2-bis[(2-propenyloxy)methyl]-1-Butanol
• CAS NO: 682-09-7
• Molecular Formula: C12H22O3
• Molecular Weight: 214.3
• EINECS: 211-661-1
• Mol File: 682-09-7.mol
• Article Data: 1

Chemical Properties

• Boiling Point: 135 °C13 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: /
• Density: 0.955 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.165mmHg at 25°C
• Refractive Index: n20/D 1.458(lit.)
• PKA: 14.62±0.10(Predicted)
• Water Solubility: Practically insoluble in water
• CAS DataBase Reference: Trimethylolpropane diallyl ether(CAS DataBase Reference)
• NIST Chemistry Reference: Trimethylolpropane diallyl ether(682-09-7)
• EPA Substance Registry System: Trimethylolpropane diallyl ether(682-09-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 2
• RTECS: TY6667000
• Hazardous Substances Data: 682-09-7(Hazardous Substances Data)

Usage

Uses

TMPAE can be used in the synthesis of isophorone diisocyanate (IPDI) based tetracene monomers which can further be used in the formation of polymer dispersed liquid crystals. It can also be used in the synthesis of allyl ether based dendrimers that find potential usage in coatings.

General Description

Trimethylolpropane diallyl ether (TMPAE) is an unsaturated allyl ether that can be synthesized by Williamson esterification reaction in the presence of trimethylolpropane, sodium hydroxide, and allyl chloride as starting materials.

InChI:InChI=1/C6H10O.C6H14/c1-3-5-7-6-4-2;1-5-6(2,3)4/h3-4H,1-2,5-6H2;5H2,1-4H3

Synthetic route

1,1,1-tri(hydroxymethyl)propane (77-99-6) + 3-chloroprop-1-ene (107-05-1) → trimethylol propane diallyl ether (682-09-7)

Conditions	Yield
With sodium hydroxide In water at 90℃; Inert atmosphere;

trimethylol propane diallyl ether (682-09-7) + 2,4,4-trimethyl-1-pentyl hypophosphorous acid (144900-28-7) → [3-(2-hydroxymethyl-2-{3-[hydroxy-(2,4,4-trimethylpentyl)phosphinoyl]propoxymethyl}butoxy)propyl]-(2,4,4-trimethylpentyl)phosphinic acid (1189189-14-7)

Conditions	Yield
With di-tert-amyl peroxide at 140℃; for 6h; Inert atmosphere;	100%

1,2-epoxytetradecane (3234-28-4) + trimethylol propane diallyl ether (682-09-7) → C37H74O5

Conditions	Yield
With potassium methanolate at 120℃; for 20.9h; Inert atmosphere;	98.2%

trimethylol propane diallyl ether (682-09-7) + C33H34O2 → C45H56O5

Conditions	Yield
With potassium methanolate at 120℃; for 21.7667h; Inert atmosphere;	97.9%

trimethylol propane diallyl ether (682-09-7) → (2,2-bis((allyloxy)methyl)butan-1-yl)dichlorophosphite

Conditions	Yield
With phosphorus trichloride In acetonitrile at -15 - 20℃; for 4h; Inert atmosphere;	88%

trimethylol propane diallyl ether (682-09-7) + 3,5-bis(2-bromo-2-methylpropanoyloxy) benzoic acid → C27H36Br2O8

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran at 20℃; for 12h;	56%

1-bromo-octane (111-83-1) + trimethylol propane diallyl ether (682-09-7) → 3,3-diallyloxymethyl-5-oxa-tridecane

Conditions	Yield
Stage #1: trimethylol propane diallyl ether With sodium In toluene at 110℃; for 4h; Stage #2: 1-bromo-octane In toluene for 6 - 10h; Heating / reflux;	55%

trimethylol propane diallyl ether (682-09-7) + 4-methoxybenzenediazonium tetrafluoroborate (459-64-3) + ammonium thiocyanate (1147550-11-5) → 2-allyloxymethyl-2-[3-(4-methoxy-phenyl)-2-thiocyanato-propoxymethyl]-butan-1-ol

Conditions	Yield
copper(II) bis(tetrafluoroborate) In water; acetone at 10 - 15℃;	35%

trimethylol propane diallyl ether (682-09-7) + ammonium thiocyanate (1147550-11-5) + 4-methylbenzenediazonium tetrafluoroborate (459-44-9) → 2-allyloxymethyl-2-(2-thiocyanato-3-p-tolyl-propoxymethyl)-butan-1-ol

Conditions	Yield
copper(II) bis(tetrafluoroborate) In water; acetone at 10 - 15℃;	35%

trimethylol propane diallyl ether (682-09-7) + ammonium thiocyanate (1147550-11-5) + benzenediazonium tetrafluoroborate (369-57-3) → 2-[(allyloxy)methyl]-2-[(3-phenyl-2-thiocyanatopropoxy)methyl]butan-1-ol

Conditions	Yield
copper(II) bis(tetrafluoroborate) In water; acetone at 10 - 15℃;	31%

trimethylol propane diallyl ether (682-09-7) + 2-methylphenyl diazonium tetrafluoroborate (2093-46-1) + ammonium thiocyanate (1147550-11-5) → 2-allyloxymethyl-2-(2-thiocyanato-3-o-tolyl-propoxymethyl)-butan-1-ol

Conditions	Yield
copper(II) bis(tetrafluoroborate) In water; acetone at 10 - 15℃;	29%

trimethylol propane diallyl ether (682-09-7) + ammonium thiocyanate (1147550-11-5) + 3-methylbenzenediazonium tetrafluoroborate (1422-76-0) → 2-allyloxymethyl-2-(2-thiocyanato-3-m-tolyl-propoxymethyl)-butan-1-ol

Conditions	Yield
copper(II) bis(tetrafluoroborate) In water; acetone at 10 - 15℃;	28%

1,6-dimercaptohexane (1191-43-1) + trimethylol propane diallyl ether (682-09-7) → polymer; monomer(s): 1,6-hexanedithiol; trimethylolpropane diallyl ether

Conditions	Yield
With benzophenone In various solvent(s) Kinetics; UV-irradiation;
With 2,2-dimethoxy-2-phenylacetophenone In various solvent(s) Kinetics; Irradiation;

trimethylol propane diallyl ether (682-09-7) + pentaerythritol tetrakis(3-mercaptopropionate) (7575-23-7) → polymer; monomer(s): pentaerythritol tetra(3-mercaptopropionate); trimethylolpropane diallyl ether

Conditions	Yield
With 2,2-dimethoxy-2-phenylacetophenone In various solvent(s) Kinetics; Irradiation;
With 2,2-dimethoxy-2-phenylacetophenone at 20℃; for 30h; UV-irradiation;

trimethylol propane diallyl ether (682-09-7) → 2,5-Diethyl-5-[((E)-propenyl)oxymethyl]-[1,3]dioxane

Conditions	Yield
tris(triphenylphosphine)ruthenium(II) chloride at 120℃; for 2h;

trimethylol propane diallyl ether (682-09-7) → C12H21Cl2O4P

Conditions	Yield
With triethylamine; trichlorophosphate In diethyl ether at -5 - 23℃; for 17.5h;

trimethylol propane diallyl ether (682-09-7) + 1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → 2,2-Bis(allyloxymethyl)-1-trimethylsiloxybutane

bi(cyclopentadiene) (77-73-6, 933-60-8, 1755-01-7) + trimethylol propane diallyl ether (682-09-7) → C14H24O3 + C22H34O3 + C32H46O3 + endo,exo,endo-pentacyclo<6.5.1.02,7.13,6.09,13>pentadeca-4,10-diene (7158-25-0)

Conditions	Yield
at 180℃;

succinic acid anhydride (108-30-5) + trimethylol propane diallyl ether (682-09-7) → C16H26O6 (174188-73-9)

Conditions	Yield
With pyridine; dmap

4-azidobutanoic acid (54447-68-6) + trimethylol propane diallyl ether (682-09-7) → C16H27N3O4 (1218771-17-5)

Conditions	Yield
With pyridine; dmap

trimethylol propane diallyl ether (682-09-7) → 3,3-bis(allyloxymethyl)-5-dihydrogen phosphoryl-5-oxa pentane

Conditions	Yield
With triethylamine; trichlorophosphate In diethyl ether at -5 - 23℃; for 17.5h;	63.8g

trimethylol propane diallyl ether (682-09-7) → 2,2-bis(3-sulfanylpropoxymethyl)butan-1-ol (57654-66-7) + C24H50O6S3 (1609547-67-2)

Conditions	Yield
With hydrogen sulfide; triethyl phosphite Concentration; Time;

trimethylol propane diallyl ether (682-09-7) + thioacetic acid (507-09-5) → C16H30O5S2

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) at 60 - 70℃; for 10h;
With 2,2-dimethoxy-2-phenylacetophenone In methanol UV-irradiation;

trimethylol propane diallyl ether (682-09-7) → C20H34O6S3

Conditions	Yield
Multi-step reaction with 4 steps 1: 2,2'-azobis(isobutyronitrile) / 10 h / 60 - 70 °C 2: hydrogenchloride / methanol; water / 3 h / Reflux 3: toluene-4-sulfonic acid / toluene / 3 h / Reflux; Dean-Stark 4: DBN / N,N-dimethyl-formamide / 0.5 h / 20 °C View Scheme

trimethylol propane diallyl ether (682-09-7) → C46H70O20S5

Conditions	Yield
Multi-step reaction with 5 steps 1: 2,2'-azobis(isobutyronitrile) / 10 h / 60 - 70 °C 2: hydrogenchloride / methanol; water / 3 h / Reflux 3: toluene-4-sulfonic acid / toluene / 3 h / Reflux; Dean-Stark 4: DBN / N,N-dimethyl-formamide / 0.5 h / 20 °C 5: DBN / N,N-dimethyl-formamide / 0.5 h / 20 °C View Scheme

trimethylol propane diallyl ether (682-09-7) → 2,2-bis(3-sulfanylpropoxymethyl)butan-1-ol (57654-66-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 2,2'-azobis(isobutyronitrile) / 10 h / 60 - 70 °C 2: hydrogenchloride / methanol; water / 3 h / Reflux View Scheme
With 2,2'-azobis(isobutyronitrile); tiolacetic acid at 20 - 70℃;	1.6 g

trimethylol propane diallyl ether (682-09-7) → trimethylolpropane bis(3-mercaptopropylether) monothioglycolate

Conditions	Yield
Multi-step reaction with 3 steps 1: 2,2'-azobis(isobutyronitrile) / 10 h / 60 - 70 °C 2: hydrogenchloride / methanol; water / 3 h / Reflux 3: toluene-4-sulfonic acid / toluene / 3 h / Reflux; Dean-Stark View Scheme

poly(methacrylic acid) (79-41-4) + trimethylol propane diallyl ether (682-09-7) → trimethylolpropane diallyl ether monomethacrylate

Conditions	Yield
With methanesulfonic acid; 4-methoxy-phenol In n-heptane at 20℃;	808 g

trimethylol propane diallyl ether (682-09-7) + 2,4-Toluene diisocyanate (584-84-9) → trimethylolpropane diallyl ether

Conditions	Yield
In toluene at 45℃;

butyl 3-mercaptopropionate (16215-21-7) + trimethylol propane diallyl ether (682-09-7) → C26H50O7S2

Conditions	Yield
With 2,2-dimethoxy-2-phenylacetophenone In methanol UV-irradiation;

Upstream product

• 77-99-6 1,1,1-tri(hydroxymethyl)propane 
• 107-05-1 3-chloroprop-1-ene 

Downstream Products

• 7158-25-0 endo,exo,endo-pentacyclo<6.5.1.0^2,7.1^3,6.0^9,13>pentadeca-4,10-diene 

Relevant articles and documents

Preparation method of trimethylolpropane diallyl ether

The invention relates to a preparation method of trimethylolpropane diallyl ether. The preparation method comprises the following steps: controlling trimethylolpropane, alkali metal hydroxide and water to form a mixture in a reactor, dropwise adding part or all of the alkali metal hydroxide into the reactor in the form of an alkali metal hydroxide aqueous solution within a preset time to form a mixture, dropwise adding chloropropene into the reactor within the preset time, and controlling the molar ratio of water to trimethylolpropane to be 1-10, wherein the molar ratio of the trimethylolpropane to the alkali metal hydroxide to the water is 1: (a-1): (b-9), 0 a a reaction product to obtain the trimethylolpropane diallyl ether. By controlling the mixed introduction mode of alkali metal hydroxide and water and controlling the molar ratio of mixed reactants, adverse factors of water areovercome, the operation is simplified, the cost is reduced, and products are easy to separate.