654636-62-1

Usage

Uses

Used in Chemical Synthesis:
3,7-Dioxa-4-aza-6-phosphanonanoic acid, 4,5-bis(1,1-dimethylethyl)-6-ethoxy-2,2-dimethyl-, 6-oxide is used as a building block in chemical synthesis for the creation of new compounds with specific properties. Its unique structure allows it to participate in various types of chemical reactions, such as esterification, amidation, and condensation, enabling the synthesis of a wide range of molecules.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, 3,7-Dioxa-4-aza-6-phosphanonanoic acid, 4,5-bis(1,1-dimethylethyl)-6-ethoxy-2,2-dimethyl-, 6-oxide is used as a potential drug candidate or as a key intermediate in the synthesis of pharmaceutical compounds. Its ability to interact with other molecules and functional groups makes it a promising candidate for the development of new drugs with specific therapeutic effects.
Used in Material Science:
3,7-Dioxa-4-aza-6-phosphanonanoic acid, 4,5-bis(1,1-dimethylethyl)-6-ethoxy-2,2-dimethyl-, 6-oxide is used in material science for the development of new materials with unique properties. Its versatile structure allows it to be incorporated into polymers, coatings, and other materials, potentially enhancing their performance and functionality.
Used in Analytical Chemistry:
In analytical chemistry, 3,7-Dioxa-4-aza-6-phosphanonanoic acid, 4,5-bis(1,1-dimethylethyl)-6-ethoxy-2,2-dimethyl-, 6-oxide can be used as a reagent or a reference compound in various analytical techniques, such as chromatography, spectroscopy, and electrochemistry. Its unique structure and properties make it suitable for the detection, separation, or quantification of other compounds in complex samples.

Synthetic route

N,N-diethyl-S-(α,α-dimethyl-α-acetic acid)dithiocarbamate (548761-51-9) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5) → N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1)

Conditions	Yield
In ethanol at 10℃; for 4.5h; UV-irradiation;	95%

2,2'-azobis(isobutyric acid) disodium salt + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5) → N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1)

Conditions	Yield
In methanol; water at 10℃; for 4.5h; UV-irradiation;	93%

N,N-diethyl-S-(α,α-dimethyl-α-acetic acid)dithiocarbamate (548761-51-9) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5) → disulfiram (97-77-8) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1)

Conditions	Yield
In ethanol at 20℃; for 4h; Product distribution / selectivity; Inert atmosphere; Photolysis;	A n/a B 90%

2-bromo-2-methylpropionic acid (2052-01-9) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5) → N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1)

Conditions	Yield
Stage #1: 2-bromo-2-methylpropionic acid; N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper; copper(I) bromide In methanol at 20℃; for 4h; Inert atmosphere; Stage #2: With hydrogenchloride In methanol; water at 12℃; pH=1.5; Product distribution / selectivity;	86%
With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper; copper(I) bromide In benzene at 20℃; for 3h;	75%
With N,N,N',N'',N'''-pentamethyldiethylenetriamine; copper; copper(I) bromide In toluene at 20℃; for 1.5h;	60%

2-methyl-2-[N-(diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionic acid, sodium salt + water (7732-18-5) → N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1)

Conditions	Yield
With hydrogenchloride In methanol; water

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C24H43N2O6P

Conditions	Yield
In tetrahydrofuran at 100℃; for 1h; Schlenk technique; Inert atmosphere;	85%

ethyl iodide (75-03-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → ethyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate (1034132-98-3)

Conditions	Yield
Stage #1: N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene Inert atmosphere; Stage #2: ethyl iodide In benzene at 20℃; for 24h; Inert atmosphere;	78%

methyl iodide (74-88-4) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → methyl 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionate

Conditions	Yield
Stage #1: N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene Inert atmosphere; Stage #2: methyl iodide In benzene at 20℃; for 24h; Inert atmosphere;	77%

2-propenoic acid 1,2 ethanediylbis(oxy-2,1-ethanediyl) ester (1680-21-3) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C46H90O18N2P2 (871982-25-1)

Conditions	Yield
In tert-butyl alcohol at 100℃; for 1h;	70%

acrylic acid n-butyl ester (141-32-2) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 2,2-dimethyl-4-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]-4-n-butoxycarbonylbutanoic acid

Conditions	Yield
In tert-butyl alcohol at 80℃; for 6h;	65%
In tert-butyl alcohol at 100℃; for 1.25h; Inert atmosphere;	45%

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) + 2-{[(4-bromo-benzenesulfonyl)-phenyl-amino]-methyl}-acrylic acid ethyl ester (647018-77-7) → 1-(4-bromo-benzenesulfonyl)-3-(2-carboxy-2-methyl-propyl)-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 12h;	62%

N-(4-benzoylphenyl)acrylamide (22421-62-1) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C33H49N2O8P (1304668-93-6)

Conditions	Yield
In tetrahydrofuran at 100℃; for 1h; Inert atmosphere;	60%

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) + 2-{[tert-butoxycarbonyl-(4-nitro-phenyl)-amino]-methyl}-acrylic acid ethyl ester → 3-(2-carboxy-2-methyl-propyl)-5-nitro-2,3-dihydro-indole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 12h;	58%

allyl bromide (106-95-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → allyl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate (1393670-68-2)

Conditions	Yield
Stage #1: N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene Inert atmosphere; Stage #2: allyl bromide In benzene at 20℃; for 24h; Inert atmosphere;	57%

4-acryloylbenzophenone + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C33H48NO9P (1304668-94-7)

Conditions	Yield
In tetrahydrofuran at 100℃; for 1h; Inert atmosphere;	55%

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) + 2-{[(4-bromo-benzenesulfonyl)-(4-methoxy-phenyl)-amino]-methyl}-acrylic acid ethyl ester (647018-78-8) → 1-(4-bromo-benzenesulfonyl)-3-(2-carboxy-2-methyl-propyl)-5-methoxy-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 18h;	54%

2-{[tert-butoxycarbonyl-(4-methoxy-phenyl)-amino]-methyl}-acrylic acid ethyl ester (647018-76-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 3-(2-carboxy-2-methyl-propyl)-5-methoxy-2,3-dihydro-indole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 18h;	48%

2-[(methyl-phenyl-amino)-methyl]-acrylic acid ethyl ester (647018-73-3) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 3-(2-carboxy-2-methyl-propyl)-1-methyl-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 12h;	47%

2-[(tert-butoxycarbonyl-phenyl-amino)-methyl]-acrylic acid ethyl ester (647018-75-5) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 3-(2-carboxy-2-methyl-propyl)-2,3-dihydro-indole-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 12h;	45%

glycinamide hydrochloride (1668-10-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C19H40N3O6P (1228178-48-0)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 1.5h; Inert atmosphere;	45%

2-{[(4-methoxy-phenyl)-methyl-amino]-methyl}-acrylic acid ethyl ester (647018-74-4) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 3-(2-carboxy-2-methyl-propyl)-5-methoxy-1-methyl-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester

Conditions	Yield
In tert-butyl alcohol at 70℃; for 12h;	38%

C52H83N12O13Pol + C9H14N4O4 (1563177-07-0) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C64H108N17O18P (1563177-09-2)

Conditions

Yield

Stage #1: C52H83N12O13Pol; N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one fluorenylmethoxycarbonyl (Fmoc) amide resin; Stage #2: C9H14N4O4 In N,N-dimethyl-formamide at 20 - 70℃; for 72.5h; fluorenylmethoxycarbonyl (Fmoc) amide resin; Inert atmosphere; Stage #3: With trifluoroacetic acid In water for 1.83333h; fluorenylmethoxycarbonyl (Fmoc) amide resin;

35%

C52H83N12O13Pol + C21H37N9O7 (1563177-08-1) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C76H131N22O21P (1563177-10-5)

Conditions

Yield

Stage #1: C52H83N12O13Pol; N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one fluorenylmethoxycarbonyl (Fmoc) amide resin; Stage #2: C21H37N9O7 In N,N-dimethyl-formamide at 20 - 70℃; fluorenylmethoxycarbonyl (Fmoc) amide resin; Inert atmosphere; Stage #3: With trifluoroacetic acid In water for 1.83333h; fluorenylmethoxycarbonyl (Fmoc) amide resin; chemoselective reaction;

30%

C52H83N12O13Pol + C15H26N6O5 + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C70H120N19O19P (1563177-12-7)

Conditions

Yield

Stage #1: C52H83N12O13Pol; N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one fluorenylmethoxycarbonyl (Fmoc) amide resin; Stage #2: C15H26N6O5 In N,N-dimethyl-formamide at 20 - 70℃; fluorenylmethoxycarbonyl (Fmoc) amide resin; Inert atmosphere; Stage #3: With trifluoroacetic acid In water for 1.83333h; fluorenylmethoxycarbonyl (Fmoc) amide resin; Temperature; Time;

15%

10-Undecen-1-ol (112-43-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → undec-10-en-1-yl 2-((tert-butyl(1-(diethoxyphosphoryl)-2,2-dimethylpropyl)amino)oxy)-2-methylpropanoate (1393670-66-0)

Conditions	Yield
With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0℃; Mitsunobu reaction;	11%

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl (188526-94-5)

Conditions	Yield
With oxygen at 120℃; Kinetics;

N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C17H35ClNO5P

Conditions	Yield
With thionyl chloride In dichloromethane at 20℃; for 2h;

sodium 4-styrenesulfonate (2695-37-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → C25H43NO9PS(1-)*Na(1+) (947705-50-2)

Conditions	Yield
In ethanol; water at 70℃; for 6h; Inert atmosphere;

1-hydroxy-pyrrolidine-2,5-dione (6066-82-6) + N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl)hydroxylamide (654636-62-1) → 2-methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]-N-propionyloxysuccinimide (1068449-32-0)

Conditions	Yield
With dicyclohexyl-carbodiimide In tetrahydrofuran at 0℃; for 1.5h;
With dicyclohexyl-carbodiimide In tetrahydrofuran at 5℃;

Upstream product

• 7732-18-5 water 
• 188526-94-5 N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)aminoxyl 
• 548761-51-9 N,N-diethyl-S-(α,α-dimethyl-α-acetic acid)dithiocarbamate 
• 2052-01-9 2-bromo-2-methylpropionic acid 

Downstream Products

• 762-04-9 Diethyl phosphonate 
• 79-31-2 isobutyric Acid 
• 227000-10-4 diethyl 2,2-dimethyl-1-(1,1-dimethylethylamino)propylphosphonate 
• 1304668-93-6 C₃₃H₄₉N₂O₈P 
• 1304668-94-7 C₃₃H₄₈NO₉P 
• 947705-50-2 C₂₅H₄₃NO₉PS^(1-)*Na⁽¹⁺⁾ 

Relevant academic research and scientific papers

Polar, steric, and stabilization effects in alkoxyamines C-ON bond homolysis: A multiparameter analysis

We present measurements of the rate constants (kd) of the C-ON bond cleavage in new alkoxyamine models containing the N-(2-methyl-2-propyl)-N-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1) moiety. The homolysis rate constants of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-and SG1-based alkoxyamines are analyzed in terms of polar inductive/field (σU), steric (σv), and radical stabilization (σRS) contributions of the leaving alkyl radicals, using a multiparameter equation, i.e., log(kd/k d,0) = ρUσU + δv + ρ RSσRS. The rate constants increase with increasing electron withdrawing, steric, and stabilization demands of the leaving alkyl radicals. Good correlations are found for TEMPO (log(kd/k d,0) = 13.6σU + 6.6v + 13.9σRS) and SG1 (log(kd/kd,0) = 19.5σU + 7.0v + 15.3σRS) derivatives, highlighting the polar sensitivity of the leaving alkyl radical to the nitroxyl moiety. Such correlations should facilitate the design of new alkoxyamines as initiators/regulators and help to improve the tuning of NMP experiments.

Synthesis of highly labile SG1-based alkoxyamines under photochemical conditions

(Chemical Equation Presented) Highly labile SG1-based alkoxyamines were synthesized using the photodecomposition of both azo compounds and dithiocarbamates. The former method was a straightforward procedure to obtain the alkoxyamines, but a high [azo]/[nitroxide] ratio is needed. The latter method required only a stoichiometric amount of dithiocarbamate and allowed the recovery of the disulfide after irradiation. This enabled combination of the two methods in a process where only 0.75 equiv of azo compound is needed and where sulfurous compounds acted only as intermediates.

PROCESS FOR PREPARING ALKOXYAMINES RESULTING FROM BETA-PHOSPHORATED NITROXIDES

The invention relates to an improved process for preparing alkoxyamines resulting from β-phosphorated nitroxides corresponding to the formula (I): by reaction with a halogenated derivative in the presence of an organometallic system. This process comprises carrying out the reaction in a water-miscible organic solvent and precipitating the alkoxyamine directly from the organic medium by adding an aqueous solution of a strong acid. These alkoxyamines can be used in particular as radical polymerizations initiators.

METHOD FOR PREPARING ALKOXYAMINES BY PHOTOLYSIS OF DITHIOCARBAMATES

The present invention relates to a novel process for preparing alkoxyamines from a nitroxide and a dithiocarbamate by photolysis reaction. This process, which does not generate effluent containing metals, may be carried out in batch or in continuous mode and takes place at a lower temperature than the known processes for synthesizing alkoxyamines.

PROCESS FOR THE PREPARATION OF THE ALKOXYAMINE 2-METHYL-2-`N-(DIETHOXYPHOSPHORYL-2,2-DIMETHYLPROPYL)-AMINOXY!PROPIONIC ACID

The present invention relates to a process for the preparation of the alkoxyamine 2-methyl-2-[N- (diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy]propionic acid or of its salts comprising a stage of saponification of an azo compound in the presence of a base, a stage of photolysis of the salt resulting from the saponification stage in the presence of N-(tert-butyl)1-diethylphosphono-2,2-dimethylpropyl nitroxide and optionally a stage of acidification of the salt of the alkoxyamine obtained on conclusion of the photolysis stage. The alkoxyamine or its salts can be used as radical polymerization initiators.

Alkoxyamines derived from beta-phosphorylated nitroxides, and use thereof for preparing polymerized or non-polymerized mono-or polyalkoxyamines

The invention relates to the use of alkoxyamines of formula (I): for the preparation of polymerized or non-polymerized mono- or polyalkoxyamines of formula (II):