35958-30-6

Usage

Uses

Antioxidant

Synthetic route

2,4-di-tert-Butylphenol (96-76-4) + acetaldehyde (75-07-0) → 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6)

Conditions	Yield
With benzenesulfonic acid In hexane for 24h; Reflux; Schlenk technique; Inert atmosphere; Glovebox;

tris(cyclopentadienyl)(tetrahydrofuran)samarium(III) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [(η5-C5H5)Sm(2,2'-ethylidene-bis(4,6-di-tert-butylphenoxo))(THF)2] (933453-74-8)

Conditions	Yield
In tetrahydrofuran (Ar, Schlenk) a THF-soln. of diphenol-compound was slowly added to a THF-soln. of complex, the mixt. was stirred overnight at room temp.; the solvent was removed under vac., toluene-soln. was concd.; elem. anal.;	95%

tricyclopentadienyl(tetrahydrofurane)neodymium + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [(η5-C5H5)Nd(2,2'-ethylidene-bis(4,6-di-tert-butylphenoxo))(THF)2] (933453-75-9)

Conditions	Yield
In tetrahydrofuran (Ar, Schlenk) a THF-soln. of diphenol-compound was slowly added to a THF-soln. of complex, the mixt. was stirred overnight at room temp.; the solvent was removed under vac., toluene-soln. was concd.; elem. anal.;	95%

methanol (67-56-1) + trimethyl indium (3385-78-2) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Me6In3(OMe)(2,2'-ethylidenebis(4,6-di-tert-butylphenolate)] (1187925-66-1)

Conditions	Yield
In methanol; diethyl ether byproducts: CH4; (N2); std. Schlenk technique; soln. of MeOH in Et2O was added to stirredsoln. of Me3In in Et2O at -76°C; warmed to room temp.; soln. of ligand in Et2O was added at 0°C; warmed to room temp.; elem. anal.;	94%

(1,4,7,10-tetraoxacyclododecane) (294-93-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → C38H61LiO6

Conditions	Yield
With n-butyllithium In hexane; toluene at 20℃; for 12h; Inert atmosphere;	94%

(η5-C5H5)3Yb(tetrahydrofuran) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [(η5-C5H5)Yb(2,2'-ethylidene-bis(4,6-di-tert-butylphenoxo))(THF)2] (933453-73-7)

Conditions	Yield
In tetrahydrofuran (Ar, Schlenk) a THF-soln. of diphenol-compound was slowly added to a THF-soln. of complex, the mixt. was stirred overnight at room temp.; the solvent was removed under vac., toluene was added to extract, -10°C; elem. anal.;	93%

titanium(IV) tetraethanolate + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Ti2(μ-OEt)2(2,2-ethylidenebis(4,6-di-tert-butylphenol)(-2H))2(OEt)2] (851091-55-9)

Conditions	Yield
In hexane byproducts: EtOH; to rapidly stirred hexane soln. of edbp (4.9 mmol) Ti(OEt)4 (4.9 mmol) added, stirred for 48 h at room temp.; filtered, washed (hexane), recrystd. (hexane/toluene 1:1) at room temp.;elem. anal.;	92%

tetrahydrofuran (109-99-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [EDBPH*K*(THF)2]

Conditions	Yield
With potassium	92%

tetrahydrofuran (109-99-9) + trimethylaluminum (75-24-1) + sodium (7440-23-5) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [(2,2-ethylidenebis(4,6-di-tert-butylphenolato))Al(CH3)2Na(tetrahydrofuran)2] (1229666-03-8)

Conditions	Yield
In tetrahydrofuran; hexane under N2; soln. of ethylidenebis(phenol) deriv. and Na in THF stirred at50°C for 4.0 h, Al(CH3)3 in hexane added slowly, mixt. stirred f or 12 h; evapn. under vac., residue dissolved in THF, hexane added, soln. filtered through Celite, filtrate stored at room temp. for several d; elem. anal.;	91%

WO[OC(CH3)3]4 (58832-09-0) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + acetonitrile (75-05-8) → [W(O)(di-phenol 2,2’-ethylidenebis(4,6-di-tertbutylphenol))2]·MeCN

Conditions	Yield
Stage #1: WO[OC(CH3)3]4; 2,2-ethylidenebis(4,6-tert-butylphenol) In diethyl ether for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: acetonitrile Inert atmosphere; Schlenk technique;	91%

tris(1,2-ethanediolate)tungsten(VI) (54153-67-2) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [C(CH3)3C6H2C(CH3)3O]2CHCH3W(OC2H4O)2

Conditions	Yield
In toluene byproducts: 1,2-ethanediol; mixed at reflux; distilled (toluene, 4 h), evapd., chromy.(silica gel-CH2Cl2), crystd.(CH3CN), dried.(vac.) 40°C for 6 h, elem. anal.;	90%

titanium(IV) isopropylate (546-68-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Ti(2,2-ethylidenebis(4,6-di-tert-butylphenol)(-2H))(O(i-Pr))2] (709671-04-5)

Conditions	Yield
In hexane byproducts: i-PrOH; to rapidly stirred hexane soln. of edbp (4.9 mmol) Ti(O(i-Pr))4 (4.9 mmol) added, stirred for 48 h at room temp.; filtered, washed (hexane), recrystd. (CH2Cl2); elem. anal.;	90%
In toluene byproducts: isopropanol; complex obtained by react. of CH3CH2(C6H2(OH)(t-Bu)2)2 and Ti(OPri)4 in toluene at 60°C for 3 h; elem. anal.; complex washed with toluene and azeotropic distilated;

18-crown-6 ether (17455-13-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → C42H69NaO8

Conditions	Yield
With sodium hexamethyldisilazane In tetrahydrofuran; toluene at 20℃; for 12h; Inert atmosphere;	90%

toluene-4-sulfonic acid 2-(2-methoxyethoxy)ethyl ester (50586-80-6) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → 2,4-di-tert-butyl-6-(1-(3,5-di-tert-butyl-2-(2-(2-methoxyethoxy)ethoxy)phenyl)ethyl)phenol (1264748-97-1)

Conditions	Yield
In N,N-dimethyl-formamide at 110℃; for 12h;	89%

tetrahydrofuran (109-99-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → (2,2'-ethylidenebis(4,6-di-tert-butylphenolato))Li∙(tetrahydrofuran)3

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h;	88%

tetrahydrofuran (109-99-9) + trimethylaluminum (75-24-1) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + sodium hydroxide (1310-73-2) → [(2,2-ethylidenebis(4,6-di-tert-butylphenolato))Al(CH3)(μ2-OH)Na(THF)3]

Conditions	Yield
In tetrahydrofuran; hexane under N2; soln. of ethylidenebis(phenol) deriv. and NaOH in THF stirred at 50°C for 12 h, Al(CH3)3 in hexane added slowly, mixt. stirred for 12 h; evapn. under vac., residue dissolved in THF, hexane added, soln. filtered through Celite, filtrate stored at room temp. for several h; elem. anal.;	88%

hexane (110-54-3) + titanium(IV) bromide (7789-68-6) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Ti(Br)2(6,6'-(ethane-1,1-diyl)bis(2,4-di-tert-butylphenolato))]*hexane

Conditions	Yield
at 60℃; for 16h; Inert atmosphere;	88%

2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → C30H45O2(1-)*Na(1+)

Conditions	Yield
With sodium In tetrahydrofuran at 20℃; for 12h; Inert atmosphere;	87%

diethylaluminium chloride (96-10-6) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → chloro-(2,2'-ethylidene-bis(4,6-di-tert-butylphenolato))aluminum(III) (251310-99-3)

Conditions	Yield
In hexane dry N2-atmosphere; addn. of Et2AlCl to ligand at 0°C, stirring for 3 h; evapn. (vac.), dissoln. in PhMe, crystn. on cooling to room temp.; elem.anal.;	86%

18-crown-6 ether (17455-13-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → C42H69KO8

Conditions	Yield
With potassium hexamethylsilazane In hexane; toluene at 20℃; for 12h; Inert atmosphere;	86%

tetrahydrofuran (109-99-9) + trimethylaluminum (75-24-1) + sodium (7440-23-5) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + benzyl alcohol (100-51-6) → [(2,2'-ethylidenebis(4,6-di-tert-butylphenol(-2H))AlMe(μ2-OBn)Na(THF)3] (1295558-43-8)

Conditions	Yield
In tetrahydrofuran EDBP-H2, AlMe3, BnOH, Na (1:1:1:1 molar ratio) in THF; NMR;	85%

diethyl ether (60-29-7) + trimethylaluminum (75-24-1) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → (diethyl ether)methyl(2,2'-ethylidenebis(4,6-di-tert-butylphenato))aluminum(III)*0.5(diethyl ether)

Conditions	Yield
In diethyl ether; toluene under N2; soln. of AlMe3 in toluene added slowly to ice cold (0°C) soln. of ligand (molar ratio 1.2:1) in Et2O; stirred for 2.5 h; dried in vac.; extd. with Et2O; filtered; filtrate concd.; cooled to -20°C; elem. anal.;	84%

trimethylaluminum (75-24-1) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → bis[methyl(2,2'-ethylidenebis(4,6-di-tert-butylphenato))aluminum(III)]

Conditions	Yield
In hexane; toluene under N2; soln. of AlMe3 in toluene added slowly to ice cold (0°C) soln. of ligand (molar ratio 1.2:1) in hexane; stirred for 2.5 h; dried in vac.; dissolved in hot (85°C) toluene; cooled to ambient temp.; elem. anal.;	84%

2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + dimethyl sulfate (77-78-1) → 2,4-di-tert-butyl-6-(1-(3,5-di-tert-butyl-2-methoxyphenyl)ethyl)phenol (1203204-44-7)

Conditions	Yield
Stage #1: 2,2-ethylidenebis(4,6-tert-butylphenol) With potassium carbonate In acetone at 20℃; for 0.5h; Stage #2: dimethyl sulfate In acetone for 48h;	84%

tetrahydrofuran (109-99-9) + neodymium trichloride (10024-93-8) + trimethylsilylmethyllithium (1822-00-0) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → bis(6,6'-(ethane-1,1-diyl)bis(2,4-di-tert-butylphenolate)NdLi(THF)3 (1350461-07-2)

Conditions	Yield
In tetrahydrofuran NdCl3 reacted with 3 equiv. of LiCH2SiMe3 in THF, treated in one portionwith ligand (2 equiv.), reacted at room temp.;	83%

18-crown-6 ether (17455-13-9) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → C42H69O8Rb

Conditions	Yield
With rubidium tert-butoxide In toluene at 20℃; for 12h; Inert atmosphere;	83%

titanium(IV) iodide (7720-83-4) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Ti(I)2(6,6'-(ethane-1,1-diyl)bis(2,4-di-tertbutylphenolate))]

Conditions	Yield
In hexane at 60℃; for 16h; Inert atmosphere;	83%

2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + benzyl alcohol (100-51-6) → 2CHCH2(C6H2OH(C4H9)2)2(1-)*2Li(1+)*2(C6H5CH2OH)

Conditions	Yield
With n-butyllithium In diethyl ether; hexane at 0℃; for 1h;	81%

tetrahydrofuran (109-99-9) + trimethylaluminum (75-24-1) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → (tetrahydrofuran)methyl(2,2'-ethylidenebis(4,6-di-tert-butylphenato))aluminum(III)

Conditions	Yield
In tetrahydrofuran; toluene under N2; soln. of AlMe3 in toluene added slowly to ice cold (0°C) soln. of ligand (molar ratio 1.2:1) in THF; stirred for 2.5 h; dried in vac.; extd. with toluene; filtered; filtrate concd.; cooled to-20°C; elem. anal.;	81%

2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) + dimethylsilicon dichloride (75-78-5) → 2,4,8,10-Tetra-t-butyl-6,6,12-trimethyl-12H-dibenzo[d,g][1,3,2]dioxasilocin (88946-12-7)

Conditions	Yield
With triethylamine In toluene Ambient temperature;	79%
With triethylamine	79%
With triethylamine In toluene for 2h; Ambient temperature;

diethyl ether (60-29-7) + iodine (7553-56-2) + trimethylaluminum (75-24-1) + 2,2-ethylidenebis(4,6-tert-butylphenol) (35958-30-6) → [Al(2,2'-ethylidenebis(4,6-di-tert-butylphenolato))I(Et2O)] (264916-84-9)

Conditions	Yield
In diethyl ether; toluene (N2); AlMe3/toluene added slowly to I2/toluene at 0°C; after 20 min, ligand/ether added, stirred for 2 h; dried (vac.), extd. (ether), concd., crystd. (cooling); elem. anal.;	79%

Upstream product

• 96-76-4 2,4-di-tert-Butylphenol 
• 75-07-0 acetaldehyde 

Downstream Products

• 199737-28-5 Mo2(NMe2)2(μ-2,2'-ethylidenebis(4,6-di-tert-butylphenolate)2) 
• 862130-14-1 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)-4-nitrophenylphosphite 
• 1203204-44-7 2,4-di-tert-butyl-6-(1-(3,5-di-tert-butyl-2-methoxyphenyl)ethyl)phenol 
• 1295558-43-8 [(2,2'-ethylidenebis(4,6-di-tert-butylphenol(-2H))AlMe(μ2-OBn)Na(THF)3] 
• 264916-85-0 [(Ph₃P=O)Al(2,2'-ethylidenebis(4,6-di-tert-butylphenolato))I] 
• 264916-86-1 [Al(2,2'-ethylidenebis(4,6-di-tert-butylphenolato))(triphenylphosphine oxide)]I 
• 1264748-97-1 2,4-di-tert-butyl-6-(1-(3,5-di-tert-butyl-2-(2-(2-methoxyethoxy)ethoxy)phenyl)ethyl)phenol 
• 1200399-00-3 [V(Np-(CF₃)C₆H₄)(2,2'-CH₃CH[4,6-(t-Bu)2C₆H₂O]2)(On-Pr)]2 
• 1199604-15-3 [V(Np-(CF₃)C₆H₄)(2,2'-CH₃CH[4,6-(t-Bu)2C₆H₂O]2)(Oi-Pr)]2 

Relevant academic research and scientific papers

Coordinating effect in ring-opening polymerization of ε-caprolactone using aluminum complexes bearing bisphenolate as catalysts

A series of Al complexes bearing diphenolate ligands was synthesized and their application for the ring-opening polymerization of ε-caprolactone was studied. Positional variation of the substituent on the aryl ring of the RCH(4,6-di-t-butylphenol)2 ligand was shown to have a considerable influence on the catalysis result. Complexes with a ortho-substituent showed greater catalytic activity than those with a para-substituent. Substitutions of an aryl moiety by H or methyl groups resulted in the catalytic activity falling between that of the ortho-substitution Al complexes and that of the para ones. Our results demonstrate that the coordinated functional group in the ortho-position of the phenyl ring could increase the catalytic activity. Moreover, X-rays of the structure and DFT analysis revealed that the coordinated functional group in the ortho-position could bridge two Al centers resulting in the transformation of a dinuclear Al complex with bridging benzyl alkoxide into a complex with terminal benzyl alkoxide, further promoting the efficacy of the initiator.

4-Formyl amino-n-methylpiperidine derivatives, the use thereof as stabilisers and organic material stabilised therewith

The present invention relates to 4-formylamino-N-methylpiperidine derivatives of the formula (I) where the variables are as defined in the Description, to a process for preparing these piperidine derivatives, to the use of these piperidine derivatives of the invention, or prepared according to the invention, for stabilizing organic material, in particular for stabilizing plastics or coating materials, and also to the use of these piperidine derivatives of the invention, or prepared according to the invention, as light stabilizers or stabilizers for wood surfaces. The present invention further relates to stabilized organic material which comprises these piperidine derivatives of the invention or prepared according to the invention.

Thioether substituted hydroxybenzophenones and stabilized compositions

2-Hydroxybenzophenone derivatives substituted in the 4′-position by a thioether moiety exhibit enhanced absorption in the UV at longer wavelength. Compositions comprising organic material subject to actinic degradation are beneficially stabilized with such derivatives.

Lubricant composition

A composition comprising a) a lubricant or a hydraulic fluid and b) at least one compound of the general formula I STR1 in which x=1 or 2 and, if x=1, R is as defined for R1 or R3 --O-- or, if x=2, R is as defined for R8, and R1 and R3 are, for example, alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, or alkyl, cycloalkyl, alkenyl, phenyl, naphthyl, aralkyl or alkaryl, which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3, or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR2 or alkyl, cycloalkyl, alkenyl, aralkyl or alkaryl which are monosubstituted or polysubstituted by groups from the series comprising halogen, cyano, nitro, e.g. --OCH3 or e.g. --COOCH3 and interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR3 and R2 is NR4 R5, --OR6 or --SR7, and R4 and R5 are identical or different and are, for example, --H, alkyl, phenyl, naphthyl, aralkyl or alkaryl, or R4 and R5, together with the N atom linking them, form, for example, a piperidine or morpholine radical, and R6 and R7 can be alkyl which may be interrupted by one or more groups from the series comprising --O--, --S--, --NH--, STR4 or are, for example, phenyl, naphthyl, alkaryl or aralkyl, and R8 can be alkylene which may be interrupted by at least one --O-- group or alkylidene which may be interrupted by at least one --O-- group. Some of the compounds of the formula I are novel. The compositions show an improved stability towards oxidative degradation, confer protection under extreme pressures and reduce frictional wear.

Amorphous modification of 1,1',1"-nitrilo(tri-2-propyl-tris-[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl] phosphite)

The new amorphous modification of 1,1',1"-nitrilo{tri-2-propyl-tris-[2,2'-ethylidene-bis(4,6-di-tert-butylphenyl)]phosphite } is obtained by cooling rapidly said compound from the melt to ambient temperature. This amorphous form is an effective process stabilizer for polyolefins, particularly polypropylene.

3,9-carbohydrate substituted 2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane phosphite stabilizers

Carbohydrate substituted phosphites of Formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.

Beta crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite]

The beta crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] is obtained by crystallizing said compound from the melt at elevated temperatures. The beta crystalline form is an effective process stabilizer for polyolefins, particularly polypropylene.

Substituted 1,4-diamino-2-butene stabilizers

N,N,N',N'-Tetrasubstituted 1,4-diamino-2-butenes where the substituents are alkyl, cycloalkyl, aralkyl, aryl or mixtures thereof provide effective antioxidant protection to lubricants and/or synthetic polymers.

Perfluoroalkyl substituted hydroxyphenylalkanoic ester antioxidants and stabilized compositions

Perfluoroalkyl substituted neopentyl alcohols can be reacted with substituted hydroxphenylalkanoic esters to form perfluoroalkyl containing hydroxyphenylalkanoic ester antioxidants. The perfluoroalkyl substituted hindered hydroxyphenyl alkanoates are stablizers which confer superior processing stability to polymers processed at elevated temperatures such as polypropylene, as well as protecting said polymers from thermal and oxidative degradation.

Carbohydrate substituted dibenzo(d,f)(1,3,2)dioxaphosphepin stabilizers

Carbohydrate substituted dibenzo[d,f][1,3,2]dioxaphosphepin compounds of formula I STR1 where A is a carbohydrate residue are effective stabilizers for polymers processed at elevated temperatures and subject to thermal or oxidative degradation.