14812-59-0

Basic information

• Product Name: 2-CHLORO-4,4,5,5-TETRAMETHYL-1,3,2-DIOXAPHOSPHOLANE
• Synonyms: 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxa-phosphol;2-CHLORO-4,4,5,5-TETRAMETHYL-1,3,2-DIOXAPHOSPHOLANE;2-Chloro-4,4,5,5-tetraMethyl-1,3,2-dioxaphospholane 95%
• CAS NO: 14812-59-0
• Molecular Formula: C₆H₁₂ClO₂P
• Molecular Weight: 182.59
• Product Categories: Catalysis and Inorganic Chemistry;Phosphorus Compounds;Phosphorus Precursors
• Mol File: 14812-59-0.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 81.5-82 °C13 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: /
• Density: 1.149 g/mL at 25 °C(lit.)
• Vapor Pressure: 2.57mmHg at 25°C
• Refractive Index: n20/D 1.471(lit.)
• CAS DataBase Reference: 2-CHLORO-4,4,5,5-TETRAMETHYL-1,3,2-DIOXAPHOSPHOLANE(CAS DataBase Reference)
• NIST Chemistry Reference: 2-CHLORO-4,4,5,5-TETRAMETHYL-1,3,2-DIOXAPHOSPHOLANE(14812-59-0)
• EPA Substance Registry System: 2-CHLORO-4,4,5,5-TETRAMETHYL-1,3,2-DIOXAPHOSPHOLANE(14812-59-0)

Safety Data

• Hazard Codes: C
• Statements: 14-34
• Safety Statements: 22-26-27-36/37/39-45
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• Hazardous Substances Data: 14812-59-0(Hazardous Substances Data)

Usage

Uses

2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) can be used:As a reagent for the phosphitylation of alcohols and heteroatomic nucleophiles, resulting in the formation of useful glycosyl donors and ligands.As a phosphitylation reagent to derivatize lignin samples for 31P NMR analysis.

InChI:InChI=1/C6H12ClO2P/c1-5(2)6(3,4)9-10(7)8-5/h1-4H3

Synthetic route

2,3-dimethyl-2,3-butane diol (76-09-5) → 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0)

Conditions	Yield
With triethylamine; phosphorus trichloride In diethyl ether at -10 - 20℃; for 2h;	70%
With triethylamine; phosphorus trichloride	34%
With pyridine; diethyl ether; phosphorus trichloride

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + N-hydroxyphthalimide (524-38-9) → 2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-isoindole-1,3-dione (138624-13-2)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃;	96%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 4,4,5,5-tetramethyl<1,3,2>dioxaphospholane-2-oxide (16352-18-4)

Conditions	Yield
With water In tetrahydrofuran for 2h;	90%
With water; triethylamine In tetrahydrofuran; benzene

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + Benzohydroxamic acid (495-18-1) → 7,7,8,8-Tetramethyl-3-phenyl-1,4,6,9-tetraoxa-2-aza-5λ5-phospha-spiro[4.4]non-2-ene (138624-18-7)

Conditions	Yield
With triethylamine In acetonitrile	90%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + tert-butyl alcohol (75-65-0) → 2-tert-butoxy-4,4,5,5-tetramethyl-[1,3,2]dioxaphospholane (28950-19-8)

Conditions	Yield
With pyridine In diethyl ether 1.) -10 deg C, 1 h, 2.) reflux, 1 h;	90%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 2-hydroxy-2-phenylacetophenone (119-53-9) → 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane

Conditions	Yield
With triethylamine In diethyl ether at -10 - 20℃; for 2h; Inert atmosphere;	90%
With triethylamine

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + C34H28O2 → (+)-(P,3S)-3-methyl-4-(4-methylphenyl)-14-[(4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yl)oxy]-1,3,6,7-tetrahydrobenzo[c]benzo[5,6]phenanthro[4,3-e]oxepine

Conditions	Yield
Stage #1: C34H28O2 With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; Inert atmosphere; Stage #2: 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane In tetrahydrofuran; mineral oil at 0 - 20℃; for 2h; Inert atmosphere;	84%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + Me3Si(1-oxo-2-pyridinone) → 1-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-1H-pyridin-2-one (138624-14-3)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃;	80%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 1-Hydroxy-2-pyridon (822-89-9) → 1-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-1H-pyridin-2-one (138624-14-3) + 2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-pyridine 1-oxide (138646-59-0)

Conditions	Yield
With triethylamine In tetrahydrofuran Title compound not separated from byproducts;	A 80% B n/a

3-O-benzyl-2-deoxy-4,6-O-(p-methoxybenzylidene)-D-glucopyranose + 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 3-O-benzyl-2-deoxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaphospholane)-4,6-O-(p-methoxybenzylidene)-D-glucopyranose + 3-O-benzyl-2-deoxy-1-(4,4,5,5-tetramethyl-1,3,2-dioxaphospholane)-4,6-O-(p-methoxybenzylidene)-D-glucopyranose

Conditions	Yield
With triethylamine In dichloromethane at -78℃; for 2h; Title compound not separated from byproducts;	A 80% B n/a

3,5-dimethyl-1H-pyrazole (67-51-6) + 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 2-(3,5-Dimethylpyrazol-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (135474-16-7)

Conditions	Yield
With triethylamine In benzene at 20℃;	75%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + potassium salt of 5-phenyltetrazole (64073-60-5) → 5-Phenyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaphospholan-2-yl)-2H-tetrazole

Conditions	Yield
In diethyl ether 1) -20 deg C, 1 h, 2) RT, 5 h;	68%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + benzoimidazole (51-17-2) → 2-(benzimidazol-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (152327-34-9)

Conditions	Yield
With triethylamine In 1,4-dioxane at 20℃; for 1h;	66%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + N1,N2-dimethyl-N1-(trimethylsilyl)benzamidine (19629-01-7) → N1,N2-dimethyl-N1-(4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yl)benzamidine (81429-22-3)

Conditions	Yield
at 20℃; for 12h;	65%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 1-hydroxy-pyrrolidine-2,5-dione (6066-82-6) → 1-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-pyrrolidine-2,5-dione (138624-12-1)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃; other hydroximides; other chlorophosphites;	65%
With triethylamine In tetrahydrofuran at 20℃;	65%

1,2,4-Triazole (288-88-0) + 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 2-(1H-1,2,4-triazol-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane

Conditions	Yield
With triethylamine In 1,4-dioxane at 20℃; for 2h;	62%

morpholine (110-91-8) + 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 4-(4,4,5,5-Tetramethyl-[1,3,2]dioxaphospholan-2-yl)-morpholine (79155-00-3)

Conditions	Yield
	60%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + sodium isocyanate (917-61-3) → 2-isocyanato-4,4,5,5-tetramethyl-[1,3,2]dioxaphospholane (72666-66-1)

Conditions	Yield
In acetonitrile; benzene for 8h; Heating;	60%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + N,N'-dimethylbenzoamidine (29019-38-3, 85522-26-5) → N1,N2-dimethyl-N1-(4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yl)benzamidine (81429-22-3)

Conditions	Yield
With triethylamine In benzene for 12h;	55%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + O-allyl-N,N-dimethyl-D-pyrrolosamine → C17H32NO5P (1187824-49-2) + C17H32NO5P (1187824-44-7)

Conditions	Yield
With triethylamine In dichloromethane at -78 - 0℃; Inert atmosphere;	A 23% B 47%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + phenyl 4,6-O-benzylidene-β-D-glucopyranoside (22887-10-1, 42821-94-3, 54502-82-8, 57783-84-3, 61169-05-9, 61169-06-0, 61221-61-2, 75829-66-2, 111137-95-2, 117677-62-0) → (2R,4aR,6S,7R,8S,8aR)-6-Phenoxy-2-phenyl-7,8-bis-(4,4,5,5-tetramethyl-[1,3,2]dioxaphospholan-2-yloxy)-hexahydro-pyrano[3,2-d][1,3]dioxine

Conditions	Yield
With pyridine In tetrahydrofuran Ambient temperature;	31%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + sodium dicarbonyl(cyclopentadienyl)ferrate → cis-(OC)(η5-Cp)Fe{μ-P(OC(CH3)2)2}2Fe(η5-Cp)(CO) + trans-(CO)(η5-Cp)Fe{μ-P(OC(CH3)2)2}2Fe(η5-Cp)(CO) + (OC)(η4-C5H6)Fe{μ-P(OCH2C(CH3)2)CH2O}2Fe(CO)3

Conditions	Yield
In tetrahydrofuran byproducts: CO; The phosphorochloridite and the iron complex were reacted at 0°C under nitrogen atm.; CO evolution; react. mixt. was stirred and allowed to warm slowly to room temp. with further stirring for 12 h; Solvent is removed in vac.; chromy. on alumina column (twice); recrystn.;	A n/a B n/a C 5%

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → ethyl tetramethylene phosphite (38206-24-5)

Conditions	Yield
With pyridine; diethyl ether; ethanol

3-methylamino-butan-2-ol (101906-02-9) + 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) → 2,2,3,3,7,8,9-heptamethyl-1,4,6-trioxa-9-aza-5λ5-phospha-spiro[4.4]nonane (38057-84-0)

Conditions	Yield
With triethylamine In benzene

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 2-(methylamino)-1-phenylethanol (68579-60-2) → 2,2,3,3,9-pentamethyl-7-phenyl-1,4,6-trioxa-9-aza-5λ5-phospha-spiro[4.4]nonane (38057-87-3)

Conditions	Yield
With triethylamine In benzene

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 2-hydroxy-N-methyl-3-methylamino-3-phenyl-propionamide (21035-18-7) → 2,2,3,3,9-pentamethyl-8-phenyl-1,4,6-trioxa-9-aza-5λ5-phospha-spiro[4.4]nonane-7-carboxylic acid methylamide (38057-83-9)

Conditions	Yield
With triethylamine In benzene

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + methanol (67-56-1) → 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-60-3)

Conditions	Yield
With N,N-dimethyl-aniline In diethyl ether
With triethylamine In diethyl ether for 2h; Ambient temperature;

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + o-tetrachloroquinone (2435-53-2) → 2,4,5,6,7-pentachloro-4',4',5',5'-tetramethyl-2λ5-spiro[benzo[1,3,2]dioxaphosphole-2,2'-[1,3,2]dioxaphospholane] (54622-78-5)

Conditions	Yield
In diethyl ether

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + 4-(vinyloxy)butan-1-ol (17832-28-9) → 4,4,5,5-tetramethyl-2-(4-vinyloxy-butoxy)-[1,3,2]dioxaphospholane (26843-31-2)

Conditions	Yield
With pyridine

2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (14812-59-0) + Diethyl phosphate (598-02-7) → 2-diethoxyphosphoryloxy-4,4,5,5-tetramethyl-[1,3,2]dioxaphospholane (61135-66-8)

Conditions	Yield
With pyridine In benzene

Upstream product

• 76-09-5 2,3-dimethyl-2,3-butane diol 

Relevant articles and documents

Chemical characterization and physical properties of solvents derived from epoxidized methyl soyate

Reactions of epoxidized methyl soyate (EMS) with alcohols, carbon dioxide, and acetone yielded liquids with solvent properties that make them more suitable than methyl soyate for dissolving polar substances. The reactions of EMS in the presence of Amberlyst-15 with alcohols, including methanol, ethanol, n-butanol, and 2-methoxyethanol, produced a series of solvents containing ether (-OR) and alcohol (-OH) groups. Reactions of EMS with carbon dioxide and acetone gave products with carbonate and ketonide functional groups, respectively. The complex mixture of compounds present in the product, EMS(MeOH), resulting from the reaction of EMS with MeOH, was characterized by MS and NMR investigations. In addition to products resulting from MeOH addition across the epoxide ring, were major amounts of cyclic tetrahydrofuran derivatives that were derived from reactions of methyl linoleate (18:2) with MeOH. All of the solvents were characterized by high boiling points and low vapor pressures. Their viscosities were higher than that of methyl soyate. Especially notable were their very high Kauributanol values, which ranged from 280 to 852, all of which are much higher than that (57) of methyl soyate. Such high KB values indicate that these solvents have very favorable solubilizing properties, which is illustrated by the ability of EMS(MeOH) to readily dissolve both polar (e.g., MeOH) and non-polar (e.g., hexane) compounds.

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