976-56-7

Basic information

• Product Name: Diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphate
• Synonyms: [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-phosphonicacidiethyl;Diethyl3,5-di-tert-buty-4-hydroxy-ben-zylphosphonate;Irganox1222;Phosphonicacid,[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-,diethylester;diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphate;DIETHYL 3,5-DI-TERT-BUTYL-4-HYDROXYBENZYLPHOSPHONATE;Antioxidant 1222;3,5-DI-TERT-BUTYL-4-HYDROXYBENZYLPHOSPHONIC ACID DIETHYL ESTER
• CAS NO: 976-56-7
• Molecular Formula: C₁₉H₃₃O₄P
• Molecular Weight: 356.44
• EINECS: 213-551-9
• Mol File: 976-56-7.mol
• Article Data: 7

Chemical Properties

• Melting Point: 122 °C
• Boiling Point: 417 °C at 760 mmHg
• Flash Point: 206 °C
• Appearance: /
• Density: 1.046 g/cm³
• Vapor Pressure: 1.51E-07mmHg at 25°C
• Refractive Index: 1.491
• Solubility: soluble in Methanol
• PKA: 12.04±0.40(Predicted)
• Water Solubility: 14mg/L at 20℃
• CAS DataBase Reference: Diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphate(976-56-7)
• EPA Substance Registry System: Diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphate(976-56-7)

Safety Data

• Hazard Codes: Xi
• Hazardous Substances Data: 976-56-7(Hazardous Substances Data)

Usage

Flammability and Explosibility

Notclassified

InChI:InChI=1/C19H33O4P/c1-9-22-24(21,23-10-2)13-14-11-15(18(3,4)5)17(20)16(12-14)19(6,7)8/h11-12,20H,9-10,13H2,1-8H3

Synthetic route

4-[(diethylamino)methyl]-2,6-bis(1,1-dimethylethyl)phenol (794-53-6) + phosphonic acid diethyl ester (762-04-9) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) + diethylamine (109-89-7)

Conditions	Yield
In toluene for 25h; Heating;	A 94% B n/a

2,6-di-tert-butyl-4-methoxymethylene-phenol (87-97-8) + triethyl phosphite (122-52-1) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
With aluminium trichloride In toluene at 110℃; for 10h;	94%

HTMP (hydroxymethylpiperidine) + 2,6-di-tert-butylphenol (128-39-2) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
With dimethyl amine; triethyl phosphite; paraformaldehyde	90%

3,5-di-tert-butyl-4-hydroxybenzyl acetate (14387-17-8) + triethyl phosphite (122-52-1) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
at 90 - 95℃; for 4h;	80%

phosphonic acid diethyl ester (762-04-9) + N,N-dimethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)amine (88-27-7) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
at 80 - 100℃; for 6h;	77%

3,5-Di-tert-butyl-4-hydroxybenzyltrimethylammonium iodide (51917-73-8) + triethyl phosphite (122-52-1) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
In xylene for 5h; Heating;	74%

N,N-dimethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)amine (88-27-7) + triethyl phosphite (122-52-1) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
at 170 - 190℃; for 5h;	40%

2,6-di-tert-butylphenol (128-39-2) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
With dimethyl amine; triethyl phosphite; Trimethylacetic acid; paraformaldehyde In Petroleum ether
With triethyl phosphite; paraformaldehyde In N,N-dimethyl-formamide	23.0 g (65%)

petroleum + 2,6-di-tert-butylphenol (128-39-2) → diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7)

Conditions	Yield
With dimethyl amine; triethyl phosphite; paraformaldehyde In acetic acid

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → O-ethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)chlorophosphonate

Conditions	Yield
With phosphorus pentachloride In toluene at 20℃; for 5h; Inert atmosphere;	89%

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonochloridate

Conditions	Yield
With phosphorus pentachloride In toluene at 30 - 60℃; for 5h; Inert atmosphere;	89%

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone (2455-14-3) + diethyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonate (128893-72-1)

Conditions	Yield
With lead dioxide In benzene for 1h; Ambient temperature;	A 5% B 86%

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → diethyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonate (128893-72-1)

Conditions	Yield
With potassium hexacyanoferrate(III) In potassium hydroxide; benzene	75%

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → α-Brom-α-(4-hydroxy-3.5-di-tert.-butyl-phenyl)methan-phosphonsaeurediethylester (128897-52-9)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane for 4h; Irradiation;	55%

trimethylsilyl bromide (2857-97-8) + diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → C21H41O4PSi2 (67344-32-5)

triethyl phosphate (78-40-0) + diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → tetraethyl (3,5-di-tert-butyl-4-hydroxyphenyl)methylenediphosphonate (58186-36-0)

Conditions	Yield
With N-Bromosuccinimide 1.) CCl4, 4 h, UV; 2.) THF, 3 h, reflux; Yield given. Multistep reaction;

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) + phosphonic acid diethyl ester (762-04-9) → tetraethyl (3,5-di-tert-butyl-4-hydroxyphenyl)methylenediphosphonate (58186-36-0)

Conditions	Yield
With sodium ethanolate; lead dioxide 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux; Yield given. Multistep reaction;

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → Diethyl 3,5-di-tert-butyl-4-hydroxy-α-piperidinobenzylphosphonate (135347-63-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 75 percent / K3Fe(CN)6 / benzene; aq. KOH 2: 84 percent / 48 h / Ambient temperature View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → O,O'-diethyl(4-hydroxy-3,5-di-tert-butyl-α-phenylaminobenzyl)phosphonate (109874-64-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 75 percent / K3Fe(CN)6 / benzene; aq. KOH 2: 94 percent / 48 h / Ambient temperature View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone (2455-14-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1) PbO2; 2) 5percent NaOEt / 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux 2: 2.5 percent / PbO2 / benzene / 1 h / Ambient temperature View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → tetraethyl (3,5-di-tert-butyl-4-hydroxyphenyl)methylenediphosphonate (58186-36-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 55 percent / N-Bromsuccinimid / CCl4 / 4 h / Irradiation 2: 81 percent / tetrahydrofuran / 3 h / Heating View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 4-Trimethylsilyloxy-3.5-di-tert.-butyl-phenylmethan-bisphosphonsaeure (128897-53-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) N-Bromsuccinimid / 1.) CCl4, 4 h, UV; 2.) THF, 3 h, reflux 2: 2.) H2O / 1.) CH2Cl2, 2 h, reflux View Scheme
Multi-step reaction with 3 steps 1: 55 percent / N-Bromsuccinimid / CCl4 / 4 h / Irradiation 2: 81 percent / tetrahydrofuran / 3 h / Heating 3: 2.) H2O / 1.) CH2Cl2, 2 h, reflux View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 4-Hydroxy-3.5-di-tert.-butyl-phenylmethan-trisphosphonsaeurehexaethylester (128911-36-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: 1) PbO2; 2) 5percent NaOEt / 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux 2: 80 percent / PbO2 / benzene / 1 h / Ambient temperature 3: 25 percent / Anilin, NaOEt / ethanol / 2 h / Heating View Scheme
Multi-step reaction with 3 steps 1: 1) PbO2; 2) 5percent NaOEt / 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux 2: 80 percent / PbO2 / benzene / 1 h / Ambient temperature 3: 71 percent / 5percent NaOEt / ethanol / 1 h / Heating View Scheme
Multi-step reaction with 2 steps 1: 1) PbO2; 2) 5percent NaOEt / 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux 2: 1) PbO2; 2) 5percent NaOEt / 1) benzene, 1 h, room temp.; 2) EtOH, 1 h, reflux View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 4-[bis(diethoxyphosphinoyl)methylene]-2,6-di-tert-butylcyclohexa-2,5-dien-1-one (125931-54-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1) PbO2; 2) 5percent NaOEt / 1) benzene; 1 h, room temp.; 2) EtOH, 1 h, reflux 2: 80 percent / PbO2 / benzene / 1 h / Ambient temperature View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid (10175-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 2: H2O View Scheme
Stage #1: diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate With trimethylsilyl bromide Stage #2: With water

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)-N,N-diethylphosphoramidoate

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphorus pentachloride / toluene / 5 h / 20 °C / Inert atmosphere 2: toluene / 30 °C / Inert atmosphere View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → ethyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]-N,N-diethylphosphoramidoate

Conditions	Yield
Multi-step reaction with 3 steps 1: phosphorus pentachloride / toluene / 5 h / 20 °C / Inert atmosphere 2: toluene / 30 °C / Inert atmosphere 3: potassium hexacyanoferrate(III); potassium hydroxide / benzene; water / 6 h / 20 °C View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → ethyl N,N-diethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonamidate

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphorus pentachloride / toluene / 5 h / 30 - 60 °C / Inert atmosphere 2: toluene / 2 h / 30 - 60 °C / Inert atmosphere View Scheme

diethyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonate (976-56-7) → ethyl N,N-diethyl[(3,5-di-t-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonamidate

Conditions	Yield
Multi-step reaction with 3 steps 1: phosphorus pentachloride / toluene / 5 h / 30 - 60 °C / Inert atmosphere 2: toluene / 2 h / 30 - 60 °C / Inert atmosphere 3: potassium hexacyanoferrate(III); potassium hydroxide / benzene / 6 h / 20 °C View Scheme

Upstream product

• 88-27-7 N,N-dimethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)amine 
• 122-52-1 triethyl phosphite 
• 14387-17-8 3,5-di-tert-butyl-4-hydroxybenzyl acetate 
• 128-39-2 2,6-di-tert-butylphenol 
• 51917-73-8 3,5-Di-tert-butyl-4-hydroxybenzyltrimethylammonium iodide 
• 87-97-8 2,6-di-tert-butyl-4-methoxymethylene-phenol 
• 762-04-9 phosphonic acid diethyl ester 
• 794-53-6 4-[(diethylamino)methyl]-2,6-bis(1,1-dimethylethyl)phenol 

Downstream Products

• 58186-36-0 tetraethyl (3,5-di-tert-butyl-4-hydroxyphenyl)methylenediphosphonate 
• 10175-90-3 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid 
• 125931-54-6 4-[bis(diethoxyphosphinoyl)methylene]-2,6-di-tert-butylcyclohexa-2,5-dien-1-one 
• 128911-36-4 4-Hydroxy-3.5-di-tert.-butyl-phenylmethan-trisphosphonsaeurehexaethylester 
• 128897-53-0 4-Trimethylsilyloxy-3.5-di-tert.-butyl-phenylmethan-bisphosphonsaeure 
• 2455-14-3 3,5,3',5'-tetra-tert-butyl-4,4'-diphenoquinone 
• 109874-64-8 O,O'-diethyl(4-hydroxy-3,5-di-tert-butyl-α-phenylaminobenzyl)phosphonate 
• 135347-63-6 Diethyl 3,5-di-tert-butyl-4-hydroxy-α-piperidinobenzylphosphonate 
• 128897-52-9 α-Brom-α-(4-hydroxy-3.5-di-tert.-butyl-phenyl)methan-phosphonsaeurediethylester 
• 128893-72-1 diethyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonate 
• 67344-32-5 C₂₁H₄₁O₄PSi₂ 

Relevant articles and documents

Process for the preparation of sterically hindered hydroxybenzylphosphonates

A process is described for the preparation of hydroxybenzylphosphonates of the formula I STR1 which involves A) reacting a phenol of the formula II STR2 with an amine of the formula III STR3 formaldehyde or paraformaldehyde and a protonic acid Hn A to give a salt of the formula IV STR4 B) distilling off the water of reaction which forms, and C) reacting the reaction mixture, or the salt IV isolated therefrom, with a trialkyl phosphite of the formula STR5 in which Hn A is an organic or inorganic acid having n protons, n is 1, 2, 3 or 4, R1 and R2 independently of one another are C1 -C12 alkyl or C5 -C7 cycloalkyl, R3 and R4 independently of one another are C1 -C12 alkyl or form, together with the nitrogen atom attached to them, a piperidyl or morpholinyl radical, and R5, R6 and R7 independently of one another are C1 -C4 alkyl; and the compounds of the formula I are suitable, for example, as processing stabilizers for plastics.

NEW SYNTHESIS OF DIALKYL(3,5-DI-tert-BUTYL-4-HYDROXYBENZYL)PHOSPHONATES

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Process for the preparation of hydroxybenzylphosphonates

A process for the preparation of compounds of the general formula I STR1 in which R1 is hydrogen or methyl, R2 and R3 independently of one another are C1 -C18 alkyl, C5 -C8 cycloalkyl, phenyl, C7 -C9 phenylalkyl or halogen, R2 is additionally hydrogen and R7 and R8 independently of one another are C1 -C18 alkyl, phenyl or C7 -C18 alkylphenyl, which comprises reacting a phenol of the formula II STR2 in which R1 to R3 have the meaning described above, with formaldehyde or paraformaldehyde, an amine of the formula III in which R4 is C1 -C4 alkyl and R5 and R6 independently of one another are hydrogen or C1 -C4 alkyl, and a phosphite of the formula IV STR3 in which R7 and R8 have the meaning described above and R9 has the meaning given for R7 and R8, at a temperature of 0°-200° C. Some compounds of the formula I are novel.