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Chemical Structure| 793-24-8 Chemical Structure| 793-24-8

Structure of 6PPD
CAS No.: 793-24-8

Chemical Structure| 793-24-8

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Product Citations

Product Citations

Zhao, Haoqi Nina ; Hu, Ximin ; Tian, Zhenyu ; Gonzalez, Melissa ; Rideout, Craig A. ; Peter, Katherine T. , et al.

Abstract: 6PPD, a tire rubber antioxidant, poses substantial ecol. risks because it can form a highly toxic quinone transformation product (TP), 6PPD-quinone (6PPDQ), during exposure to gas-phase ozone. Important data gaps exist regarding the structures, reaction mechanisms, and environmental occurrence of TPs from 6PPD ozonation. To address these data gaps, gas-phase ozonation of 6PPD was conducted over 24-168 h and ozonation TPs were characterized using high-resolution mass spectrometry. The probable structures were proposed for 23 TPs with 5 subsequently standard-verified. Consistent with prior findings, 6PPDQ (C18H22N2O2) was one of the major TPs in 6PPD ozonation (~1 to 19% yield). Notably, 6PPDQ was not observed during ozonation of 6QDI (N-(1,3-dimethylbutyl)-N'-phenyl-p-quinonediimine), indicating that 6PPDQ formation does not proceed through 6QDI or associated 6QDI TPs. Other major 6PPD TPs included multiple C18H22N2O and C18H22N2O2 isomers, with presumptive N-oxide, N,N'-dioxide, and orthoquinone structures. Standard-verified TPs were quantified in roadway-impacted environmental samples, with total concentrations of 130 ± 3.2μg/g in methanol extracts of tire tread wear particles (TWPs), 34 ± 4μg/g-TWP in aqueous TWP leachates, 2700 ± 1500 ng/L in roadway runoff, and 1900 ± 1200 ng/L in roadway-impacted creeks. These data demonstrate that 6PPD TPs are likely an important and ubiquitous class of contaminants in roadway-impacted environments.

Keywords: 6PPD ; 6QDI ; ozone ; air ; N-oxide ; tire tread wear particles ; roadway environments

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Product Details of [ 793-24-8 ]

CAS No. :793-24-8
Formula : C18H24N2
M.W : 268.40
SMILES Code : CC(NC1=CC=C(NC2=CC=CC=C2)C=C1)CC(C)C
English Name :N1-(4-Methylpentan-2-yl)-N4-phenylbenzene-1,4-diamine
MDL No. :MFCD00072248
InChI Key :ZZMVLMVFYMGSMY-UHFFFAOYSA-N
Pubchem ID :13101

Safety of [ 793-24-8 ]

Computational Chemistry of [ 793-24-8 ] Show Less

Physicochemical Properties

Num. heavy atoms 20
Num. arom. heavy atoms 12
Fraction Csp3 0.33
Num. rotatable bonds 6
Num. H-bond acceptors 0.0
Num. H-bond donors 2.0
Molar Refractivity 89.33
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

24.06 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

3.49
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

5.57
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

5.09
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

4.2
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

3.93
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

4.46

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-5.06
Solubility 0.00233 mg/ml ; 0.00000869 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-5.84
Solubility 0.000391 mg/ml ; 0.00000146 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Moderately soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-6.68
Solubility 0.0000558 mg/ml ; 0.000000208 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Poorly soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

High
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

Yes
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

Yes
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

Yes
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

Yes
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-3.98 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

1.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

1.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

1.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

0.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

2.48

Application In Synthesis of [ 793-24-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 793-24-8 ]

[ 793-24-8 ] Synthesis Path-Downstream   1~14

  • 1
  • [ 108-10-1 ]
  • [ 101-54-2 ]
  • [ 793-24-8 ]
YieldReaction ConditionsOperation in experiment
100% With hydrogen at 99.84℃; for 4h; Autoclave;
99.4% With hydrogen; pyrographite at 20 - 150℃; for 0.1h; Autoclave; 1 (Production Example 2 of antioxidant from aniline (Method of synthesis of antioxidant 6PPD-1 in Table 1)) Two molecules of the acetone synthesized above (Method 1-2 of preparing acetone without using petroleum resources) were subjected to an aldol condensation reaction to synthesize diacetone alcohol. The diacetone alcohol was then easily dehydrated to be converted to mesityl oxide. The mesityl oxide was hydrogenated with a palladium catalyst to synthesize methyl isobutyl ketone. [0126] The following reaction was performed using the biomass-derived aniline obtained by the above method and nitrobenzene generated in that process. Meanwhile, nitrobenzene may be synthesized by oxidation of a part of the biomass-derived aniline according to a known method. An amount of 187 g of a 25% aqueous tetramethylammonium hydroxide solution (TMAOH) was concentrated by distillation at a temperature of 55°C under a pressure of 75 mbar to give a 35% solution. After addition of the biomass-derived aniline (269 mL) to the solution, the aniline/water azeotrope was evaporated at a temperature of 75°C under a pressure of 75 mbar until the molar ratio of water/base reached about 4:1. Subsequently, 60 g of the nitrobenzene was added and the resulting mixed solution was further stirred for four hours, while distillation of the water/aniline azeotrope was continued. To the crude mixed solution were added 2.2 g of a Pt/C catalyst (5% Pt) and 120 mL of water. Next, at a temperature of 80°C, the pressure was increased to the maximum of 15 bar with hydrogen, and then the reaction mixture was stirred until no further absorption of hydrogen was found. To the resulting mixture was added 100 mL of toluene, and the catalyst was removed by filtration, followed by separation of the mixture into an organic phase and a water phase with a separatory funnel. Then, purification of the organic phase by fractional distillation gave 4-aminodiphenylamine in a yield of 91%. An amount of 129.3 g of the 4-aminodiphenylamine, 120.2 g of methyl isobutyl ketone synthesized above, 0.77 g of a platinum catalyst (5% Pt on carbon sulfide powder (hydrous product), water content: 55.26% by mass, produced by N.E. Chemcat Corporation), and 0.65 g of activated carbon (Taiko activated carbon S-type, produced by Futamura Chemical Co., Ltd.) were introduced into a stirring autoclave and exposed to a hydrogen atmosphere. Then, the inside temperature of the autoclave was raised from room temperature to 150°C over about one hour. Subsequently, the hydrogen pressure was increased to 30 kgf/cm2 (2.94 MPa), and a reaction was allowed to proceed at the same temperature and the same pressure while feeding the consumed amount of hydrogen. After two hours from the start of increasing the hydrogen pressure, hydrogen was released from the autoclave to decrease the pressure to normal pressure, while the reaction solution was cooled to room temperature. The reaction solution was filtrated to remove the catalyst and the activated carbon. The resulting reaction product was subjected to separation by high performance liquid chromatography to give No.41 4-(1,3-dimethylbutylamino)diphenylamine (antioxidant 6PPD-1) in a yield of 99.4%.
With platinum on activated charcoal; isopropyl alcohol at 50 - 150℃; Hydrogenation;
With hydrogen at 135 - 145℃; Industry scale; 3 EXAMPLE 3; In a reactor for making the antidegradant, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine, a copper catalyst having the same composition as Example 1 in the amount of 8 tons is loaded. After the reactor is tested for air-tightness and pressure, nitrogen gas is fed into the reactor and eventually filled up the reactor with the pressure being maintained at 2.5 MPa. The air circulator is started. Then, the reactor is started to be heated, and the temperature increases at a velocity of about 10-15° C./hr. When the temperature reaches 110° C., the catalyst is maintained at that temperature for 4-6 hours to completely remove the water from the copper catalyst.Then, hydrogen gas is fed to the reactor. It is then observed that the temperature in the reactor rises from the heat emitted by the reaction. The temperature of the copper catalyst bed is controlled and monitored as well as the pressure and temperature of the system. The overheating of the catalyst bed caused by the heat emitted from the hydrogenation reaction should be avoided. Initially, the hydrogen gas flow is 0.5% by volume of the total gas flow. As the reductive hydrogenation of the copper-based catalyst proceeds, the volume percentage of the hydrogen gas is increased gradually. The reaction is being constantly observed, and once the concentration of the hydrogen gas flow remains the same in the feed and at the outlet, the reductive hydrogenation step has concluded and activated copper catalyst is obtained. Alternatively, the count on the meter for the hydrogen gas through the inlet into the reactor is recorded and the actual amount of hydrogen gas that enters the reactor is calculated in comparison with the theoretical amount of hydrogen gas that needs to be consumed in order to hydrogenate the fed copper oxide. When the actually consumed hydrogen gas is about the same as the theoretical value of the hydrogen consumption, coupled with the fact that the concentration of the hydrogen gas before and after flowing through the catalyst bed remains the same, then, it is confirmed that the hydrogenation activation is complete and the activated catalyst goes into the next step of passivation.Next, the temperature of the reactor is lowered to 135-145° C., and a liquid mixture of 2,4-dichloroaniline dissolved in isopropanol is fed into the reactor at a flow rate of 1000 L/hr. The amount of chlorine in the liquid mixture is 3000 PPM. The passivation step is complete after 24 hours of treatment.Then, the copper-based catalyst is ready for production. The reactor is adjusted to have a hydrogen gas pressure of about 6 MPa. A liquid mixture of 4-aminodiphenylamine made by the nitrobenzene method and MIBK is fed at a molar ratio of 1:1.8 to make the final product, N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine. The final product is tested at the outlet. The weight percentage of 4-aminodiphenylamine in the product is 0.5%, and the weight percentage of the product is 97.6%. As indicated in this example, the activity and selectivity of the pretreated copper catalyst quickly becomes stabilized for the alkylation reaction.
With 3 % platinum on carbon; hydrogen at 155℃; for 0.5h; Autoclave; 7 EXAMPLE 7 - Conversion of 4-ADPA to 6PPD This example illustrates conversion of 4-ADPA (purity >99%) obtained from the process of Example 6 above to N-(l,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), a useful antiozonant for protection of rubber products. 4-ADPA (235.5 gm), methyl isobutyl ketone (MIBK) (177 gm) and 3% Pt/C catalyst (1.2 gm) along with activated charcoal (4.8 grams) was charged into a 1 liter Parr autoclave. After purging with hydrogen the reaction mixture was heated to 155°C under a hydrogen pressure of 35 kg/cm . At the end of reduction (about 0.5 hr, typically 4-ADPA 0.25% by GC analysis), the reaction mixture was cooled and filtered to separate it from the catalyst mass. A 6PPD product of 99.2% purity, as measured by GC, was obtained after distillation of water and MIBK. The same Pt/C catalyst was used for 3 recycles with a maximum alkylation time up to 70 minutes indicating that 4-ADPA obtained from the above process of Example 6 is of good quality since the Pt/C catalyst is not adversely affected by the by-products in the 4-ADPA product during the reduction reaction.
With Pd/C; hydrogen at 200℃;
With hydrogen at 200℃; for 4h; Autoclave;
With platinum on carbon; hydrogen at 115℃; 1-7 Example 1 The 0.3% platinum carbon catalyst was loaded into the fixed bed reaction device, the nitrogen was filled with 0.2MPa pressure and replaced the entire fixed bed reaction system, after the reaction system was replaced, the temperature was heated up, the hydrogen flow rate was 0.2L/min, and the synthesis test of 6PPD was carried out under the conditions of temperature 115 °C, pressure 1.1 MPa, material ketoamine ratio 3.5:1, hydrogen-oil ratio 2000:1, and the RT conversion rate was 99.6%, 6PPD selectivity was 99.42%, and the ketone alcohol ratio was 99/1, product purity 99.06%.
With hydrogen; 0.3 % platinum on carbon at 115℃; 1; 3; 6-7 Example 1 The 0.3% platinum carbon catalyst was loaded into the fixed bed reaction device, the nitrogen was filled with 0.2MPa pressure and replaced the entire fixed bed reaction system, after the reaction system was replaced, the temperature was heated up, the hydrogen flow rate was 0.2L/min, and the synthesis test of 6PPD was carried out under the conditions of temperature 115 °C, pressure 1.1 MPa, material ketoamine ratio 3.5:1, hydrogen-oil ratio 2000:1, and the RT conversion rate was 99.6%, 6PPD selectivity was 99.42%, and the ketone alcohol ratio was 99/1, product purity 99.06%.

  • 2
  • [ 870-23-5 ]
  • [ 793-24-8 ]
  • [ 823805-08-9 ]
YieldReaction ConditionsOperation in experiment
65% Stage #1: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine With magnesium sulfate; silver(l) oxide In toluene at 25℃; for 15h; Stage #2: prop-2-ene-1-thiol In ethanol at 25℃;
  • 3
  • [ 793-24-8 ]
  • [ 74-88-4 ]
  • [ 118745-59-8 ]
YieldReaction ConditionsOperation in experiment
With carbon disulfide; sodium hydroxide In tetrahydrofuran 14 Preparation of N-(4-anilinophenyl)-N-(1,3-dimethyl-butyl)-dithiocarbamate methyl ester EXAMPLE 14 Preparation of N-(4-anilinophenyl)-N-(1,3-dimethyl-butyl)-dithiocarbamate methyl ester N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (26.8g, 0.10 mol) is dissolved in 100 mL tetrahydrofuran in a 250 mL, 3-neck round bottom flask. Carbon disulfide (7.6g, 0.10 mol) is added over 0.5 hours with the concurrent addition of an aqueous solution of sodium hydroxide (4.0g, 0.10 mol). When addition is complete, methyl iodide (14.2g, 0.10 mol) is added and the mixture refluxed for 1 hour. The solvent is then stripped off on a rotary evaporator and the residue extracted with methylene chloride. The extract is dried with MgSO4 and the solvent is again removed on the rotary evaporator to yield the product.
  • 4
  • [ 872-05-9 ]
  • [ 793-24-8 ]
  • [ 941703-37-3 ]
YieldReaction ConditionsOperation in experiment
With tetrabutylammomium bromide at 160 - 170℃; for 27h; 1 Example 1; A 1-L, 4-necked round bottomed flask equipped with a mantle, temperature controller, thermocouple, and pressure equilibrated dropping funnel was charged under nitrogen positive pressure with soid N-'-phenyl-N-2-isohexyl-p-phenylenediamine (53.38 g, 0.1989 mole) commercially available as Flexzone 7P from Chemtura Corp., aluminum chloride (13.37 g, 0.100 mole, 50.4 mole % relative to N'-phenyl-N-2-isohexyl-p-phenylenediamine) and tetra-n-butylammonium bromide (21.34 g, 0.0661 mole, 33.3 mole % relative to N'-phenyl-N-2-isohexyl-p-phenylenediamine). Stirring was started at ca. 200-300 rpm and the mixture warmed to 160° C. When the dark brown-black reaction mixture had reached 160° C., 94% 1-decene (97.64 g, 0.696 mole, 3.5 equiv. relative to N'-phenyl-N-2-isohexyl-p-phenylenediamine) was added over 2 hr. The reaction mixture was brought to 170° C. upon completion of the addition and maintained at this temperature for 25 hr. The reaction product was then allowed to cool down to ambient temperature and was diluted with 300 mL n-heptane. The dark brown-black reaction mixture separated into a lower solid phase and an upper liquid phase, which was decanted into a 2-L separatory funnel, washed with 2×500 mL water and then 400 mL water-100 mL conc. aqueous ammonia, and then dried over anhydrous sodium sulfate. The solid phase at the bottom of the flask weighed 50.74 g. The drying agent was removed from the product by suction filtration through a 9.0 cm diameter disk of 934 AH glass fiber paper. The dark filtrate was then condensed in vacuo (rotary evaporator, 95° C. water bath, <5 mm final vacuum) to obtain 49.49 g of a dark brown-black oil. GC analysis of the oil indicated that it was a mixture of (area %) 17.1% unreacted N'-phenyl-N-2-isohexyl-p-phenylenediamine, 71.8% mono-decylated N'-phenyl-N-2-isohexyl-p-phenylenediamine and 7.5% multi-decylated N'-phenyl-N-2-isohexyl-p-phenylenediamine. The monodecylated product was a mixture of two isomers: 8.2% and 63.6%. The major isomer was isolated by column chromatography. The major isomer was identified as N'-phenyl-N-2-isohexyl-[2-(2-isodecyl)-p-phenylene)]diamine (GRFE) by its GC retention time, IR spectra and NMR spectra, which were consistent with the GC retention time, IR spectra and NMR spectra of an authentic GRFE sample prepared using a different synthesis route, i.e., from 1-decene using diethyl aluminum chloride as a catalyst, heat and high pressure.
  • 5
  • [ 793-24-8 ]
  • [ 20170-32-5 ]
  • [ 1783885-08-4 ]
YieldReaction ConditionsOperation in experiment
With boric acid In toluene for 15h; Dean-Stark; Inert atmosphere; Reflux; 6 Example 6: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid Example 6: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid In a set-up of Dean-Stark apparatus, 1.0 g of N-(l ,3-Dimethyl-butyl)-N'-phenyl- benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-ditert-butyl- 4-hydroxyphenyl) propanoic acid and a catalytic amount of boric acid (0.024g) are added to the flask. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3- dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamide.
  • 6
  • [ 793-24-8 ]
  • [ 6386-38-5 ]
  • [ 1783885-08-4 ]
YieldReaction ConditionsOperation in experiment
With boric acid In toluene for 15h; Dean-Stark; Inert atmosphere; Reflux; Molecular sieve; 10 Example 10: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid methyl ester Example 10: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l ,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- pheny I) -propionic acid methyl ester In a set-up of Dean-Stark apparatus, 1.0 g of N-(l ,3-Dimethyl-butyl)-N'-phenyl- benzene- 1 ,4-diamine is dissolved in 40 ml of anhydrous toluene. 1.3 g of 3-(3,5-Di-tert-butyl- 4-hydroxy-phenyl)-propionic acid methyl ester and a catalytic amount of boric acid (0.024g) are added to the flask. 10 g of 4 A0 molecular sieves are added in the dean stark to absorb the eliminated methanol during the course of reaction. The reaction mixture is refluxed under argon atmosphere for 15 hours. The crude product thus obtained is purified to get 3-(3,5-Di- tert-butyl-4-hydroxy-phenyl)-N-( 1 ,3 -dimethyl-butyl)-N-(4-phenylamino-phenyl)- propionamide.
  • 7
  • [ 108-77-0 ]
  • [ 36294-23-2 ]
  • [ 793-24-8 ]
  • [ 1783885-14-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-(3-hydroxypropyl)-2,6-di-tert-butylphenol With triethylamine In tetrahydrofuran at 0℃; for 4h; Inert atmosphere; Stage #2: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine In tetrahydrofuran at 65℃; for 15h; Inert atmosphere; 21 Example 21: Synthesis of 4-[3-({4,6-bis[ (4-anilinophenyl)(l,3- dimethylbutyl) amino] -1 ,3, 5-triazin-2-yl}oxy)propyl] '-2, 6-ditert-butylphenol using 2,4, 6- Trichloro-f 1, 3, 5]triazine Example 21: Synthesis of 4-[3-({4,6-bis[ (4-anilinophenyl)(l,3- dimethylbutyl) amino] -1 ,3, 5-triazin-2-yl}oxy)propyl] '-2, 6-ditert-butylphenol using 2,4, 6- Trichloro-f 1, 3, 5]triazine In a 100 ml of 3 -neck round bottom flask, 1.0 g of 2,4,6-Trichloro-[l ,3,5]triazine is dissolved in 25 ml of anhydrous tetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bath maintained at 0°C using salt. 3.1 ml of triethyl amine is added. 1.6g of 2,6-Di-tert- butyl-4-(3-hydroxy-propyl)-phenol is transferred to the round bottom flask under nitrogen atmosphere. It is stirred for 4 hours at 0°C. Now 3.1g of N-(l ,3-Dimethyl-butyl)-N'-phenyl- benzene-l ,4-diamine is transferred to the round bottom flask under nitrogen atmosphere. Reactants are heated to reflux temperature of tetrahydrofuran (65°C). The reaction is completed in 15 hours. The crude product thus obtained is purified to get 4-[3-({4,6-bis[(4- anilinophenyl)(l ,3-dimethylbutyl)amino]-l , 3, 5-triazin-2-yl}oxy)propyl]-2, 6-ditert- butylphenol.
  • 8
  • [ 108-77-0 ]
  • [ 36294-23-2 ]
  • [ 793-24-8 ]
  • [ 1783885-15-3 ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1,3,5-trichloro-2,4,6-triazine; N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine With triethylamine In tetrahydrofuran at 0℃; for 4h; Inert atmosphere; Stage #2: 4-(3-hydroxypropyl)-2,6-di-tert-butylphenol In tetrahydrofuran at 65℃; for 15h; Inert atmosphere; 22 Example 22: Synthesis of 4- [3-({4- [(4-anilinophenyl) (1 ,3-dimethylbutyl)amino] -6- [3-(3, 5-ditert-butyl-4-hydroxyphenyl)-propoxy] - 1 , 3, 5-triazin-2-yl}oxy)propyl] -2, 6-ditert- butylphenol using 2,4, 6-Trichloro-fl,3,5Jtriazine Example 22: Synthesis of 4- [3-({4- [(4-anilinophenyl) (1 ,3-dimethylbutyl)amino] -6- [3-(3, 5-ditert-butyl-4-hydroxyphenyl)-propoxy] - 1 , 3, 5-triazin-2-yl}oxy)propyl] -2, 6-ditert- butylphenol using 2,4, 6-Trichloro-fl,3,5Jtriazine In a 100 ml of 3 -neck round bottom flask, 1.0 g of 2,4,6-Trichloro-[l ,3,5]triazine is dissolved in 25 ml of anhydrous tetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bath maintained at 0°C using salt. 3.1 ml of triethyl amine is added. Ug of N-(l ,3- Dimethyl-butyl)-N'-phenyl-benzene-l ,4-diamine is transferred to the round bottom flask under nitrogen atmosphere. It is stirred for 4 hours at 0°C. Now 3.0g of 2,6-Di-tert-butyl-4- (3-hydroxy-propyl)-phenol is transferred to the round bottom flask under nitrogen atmosphere. Reactants are heated to reflux temperature of tetrahydrofuran (65°C). The reaction is completed in 15 hours. The crude product thus obtained is purified to get 4-[3-({4- [(4-anilinophenyl)( 1 ,3 -dimethylbutyl)amino] -6-[3 -(3 ,5 -ditert-butyl-4-hydroxyphenyl)- propoxy ] -1 ,3 ,5 -triazin-2-y 1 } oxy)propy 1] -2 , 6-ditert-buty lphenol .
  • 9
  • [ 96-18-4 ]
  • [ 36294-23-2 ]
  • [ 793-24-8 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1,2,3-trichloropropane; N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine With triethylamine In tetrahydrofuran at 0℃; for 10h; Inert atmosphere; Stage #2: 4-(3-hydroxypropyl)-2,6-di-tert-butylphenol In tetrahydrofuran at 110℃; for 5h; Inert atmosphere; 25 Example 25: Synthesis of 2, 6-Di-tert-butyl-4-[3-(2-[ (1 ,3-dimethyl-butyl)-(4- phenylamino-phenyl)-amino] - 1-{ [(1 ,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino] - methyl} -ethoxy) -propyl] -phenol using 1,2,3-Trichloro-propane Example 25: Synthesis of 2, 6-Di-tert-butyl-4-[3-(2-[ (1 ,3-dimethyl-butyl)-(4- phenylamino-phenyl)-amino] - 1-{ [(1 ,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino] - methyl} -ethoxy) -propyl] -phenol using 1,2,3-Trichloro-propane In a 100 ml of 3-neck round bottom flask, 1.0 g of 1 ,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous tetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bath maintained at 0°C using salt. 3.2 ml of triethyl amine is added. 3.1g of N-(l ,3- Dimethyl-butyl)-N'-phenyl-benzene-l ,4-diamine is transferred to the round bottom flask under nitrogen atmosphere. It is stirred for 10 hours at 0°C. Now 1.5g of 2,6-Di-tert-butyl-4- (3-hydroxy-propyl)-phenol is transferred to the round bottom flask under nitrogen atmosphere. Reactants are heated to reflux temperature of toluene (1 10°C). The reaction is completed in 5 hours. The crude product thus obtained is purified to get 2,6-Di-tert-butyl-4- [3 -(2- [( 1 ,3 -dimethyl-butyl)-(4-phenylamino-phenyl)-amino] - 1 - { [( 1 ,3 -dimethyl-butyl)-(4- phenylamino-phenyl)-amino]-methyl}-ethoxy)-propyl]-phenol.
  • 10
  • [ 96-18-4 ]
  • [ 36294-23-2 ]
  • [ 793-24-8 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1,2,3-trichloropropane; 4-(3-hydroxypropyl)-2,6-di-tert-butylphenol With triethylamine In tetrahydrofuran at 0℃; for 10h; Inert atmosphere; Stage #2: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine In tetrahydrofuran at 110℃; for 5h; Inert atmosphere; 26 Example 26: Synthesis of 4-[3-({3-[(4-anilinophenyl)(l,3-dimethylbutyl)amino]-5- [3-(3 ,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl] -2 ,6-ditert-butylphenol using 1,2,3-Trichloro-propane Example 26: Synthesis of 4-[3-({3-[(4-anilinophenyl)(l,3-dimethylbutyl)amino]-5- [3-(3 ,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl] -2 ,6-ditert-butylphenol using 1,2,3-Trichloro-propane In a 100 ml of 3-neck round bottom flask, 1.0 g of 1 ,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous toluene under nitrogen atmosphere. Flask is kept in ice bath maintained at 0°C using salt. 3.2 ml of triethyl amine is added. 3.0g of 2,6-Di-tert-butyl-4-(3- hydroxy-propyl)-phenol is transferred to the round bottom flask under nitrogen atmosphere. It is stirred for 10 hours at 0°C. Now 1.6g of N-(l ,3-Dimethyl-butyl)-N'-phenyl-benzene-l ,4- diamine is transferred to the round bottom flask under nitrogen atmosphere. Reactants are heated to reflux temperature of toluene (1 10°C). The reaction is completed in 5 hours. The crude product thus obtained is purified to get 4-[3-({3-[(4-anilinophenyl)(l ,3- dimethylbutyl)amino]-5-[3-(3,5-difert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl]- 2 , 6-ditert-buty lphenol .
  • 11
  • [ 96-18-4 ]
  • [ 793-24-8 ]
  • [ 1783885-16-4 ]
YieldReaction ConditionsOperation in experiment
4.8 g With triethylamine In toluene at 110℃; for 20h; Inert atmosphere; 23 Example 23: Synthesis ofN, N ',N"-Tris-( 1,3 -dimethyl-butyl) -N, N', N"-tris-(4- phenylamino-phenyl) -propane- 1 , 2, 3-triamine using 1, 2, 3-Trichloro-propane Example 23: Synthesis ofN, N ',N"-Tris-( 1,3 -dimethyl-butyl) -N, N', N"-tris-(4- phenylamino-phenyl) -propane- 1 , 2, 3-triamine using 1, 2, 3-Trichloro-propane In a 100 ml of 3 -neck round bottom flask, 1.0 g of 1 ,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous toluene under nitrogen atmosphere. 3.0 ml of triethyl amine is added. 5.8g of N-(l ,3-Dimethyl-butyl)-N'-phenyl-benzene-l ,4-diamine is transferred to the round bottom flask under nitrogen atmosphere. Reactants are heated to reflux temperature of toluene (1 10°C). The reaction is completed in 20 hours. The crude product thus obtained is purified to get 4.8g of N, N',N"-Tris-(l ,3-dimethyl-butyl)-N, N N"-tris-(4-phenylamino- phenyl)-propane-l ,2,3-triamine
  • 12
  • [ 793-24-8 ]
  • [ 3062-64-4 ]
  • [ 1783885-08-4 ]
YieldReaction ConditionsOperation in experiment
1.5 g With triethylamine In toluene at 111℃; for 5h; Inert atmosphere; 2 Example 2: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- phenyl)-propionyl chloride Example 2: Synthesis of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(l,3-dimethyl- butyl)-N-(4-phenylamino-phenyl)-propionamide using 3-(3,5-Di-tert-butyl-4-hydroxy- phenyl)-propionyl chloride In a 100 ml of 3-neck round bottom flask, 1.0g of N-(l ,3-Dimethyl-butyl)-N'- phenyl-benzene-l ,4-diamine was dissolved in 20 ml of anhydrous toluene under argon atmosphere. 0.75 ml of triethyl amine was added drop wise. 1.4 g of 3-(3,5-Di-tert-butyl-4- hydroxy-phenyl)-propionyl chloride was dissolved in 20 ml of anhydrous toluene and was transferred drop wise to the round bottom flask containing N-(l ,3-Dimethyl-butyl)-N'- phenyl-benzene-l ,4-diamine under argon atmosphere. Reactants were heated to reflux temperature of toluene (1 1 1°C). The reaction was completed in 5 hours. The crude product thus obtained was purified by washing with cold hexane to get 1.5g of 3-(3,5-Di-tert-butyl-4- hydroxy-phenyl)-N-(l ,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamide and the structure was confirmed by 500 MHz 1H NMR with peaks appearing at 0.9-1.1 (m), 1.42 (s), 1.61 (m), 1.94 (m), 2.28 (t), 2.83 (t), 3.89 (m), 6.83 (m), 6.88 (s), 7.03 (m), 7.13-7.15 (m), 7.32-7.35 (m) ppm.
  • 13
  • [ 950-59-4 ]
  • [ 793-24-8 ]
  • [ 142-28-9 ]
  • [ 1831959-45-5 ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate In benzene at 85℃; for 3h; Inert atmosphere; II-5 Example II-5 Example II-5 Under the protective atomosphere of nitrogen gas, to a 250ml four-necked flask equiped with a stirrer, a thermometer,a condensing tube and a dropping funnel, there were added 20.23g (85mmol) 2,6-di-tert-butyl-4-mercaptophenol,12.99g (115mmol) 1,3-dichloropropane, 18.49g (69mmol) N-(1,3-dimethyl butyl)-N’-phenyl p-phenylene diamine,0.76g (7.2mmol) sodium carbonate and 150mL benzene, rapidly stirred, reacted at 85 degrees Celsius for 3h. Upon completion of the reaction, the solvent and water (generated during the reaction) were removed by vacuum distillation, the titled hindered phenol compound was obtained by using column chromatography. The compound was characterized as follows : 1H NMR (300MHz, CDCl3) : δ 0.80 (6H), 1.11-1.21 (5H), 1.36 (18H), 1.67 (1H), 2.16-3.47 (6H), 5.32 (1H), 6.80-7.17(7H), 7.55 (1H); 13C NMR (75MHz, CDCl3) : δ 22.4, 24.6, 34.6, 45.2, 52.7, 58.6, 115.4, 116.6, 119.4, 121.8, 126.2, 129.5, 136.6,144.1, 153.5;C35H50N2OS (calculated) : : C 76.87, H 9.22, N 5.12, O 2.93, S 5.86; (measured) : C 76.95, H 9.28, N 5.08, O 2.87,S 5.80.
With sodium carbonate In benzene at 85℃; for 3h; Inert atmosphere; 5 Under nitrogen atmosphere, equipped with a stirrer, a thermometer, a condenser and a dropping funnel 250ml four-necked flask was added 20.23 g (85mmol) 2,6- di-tert-butyl-4-mercapto-phenol, 12.99 g (115mmol ) 1,3-dichloropropane, 18.49 g (69mmol) N- (1,3- dimethylbutyl) -N'-phenyl-p-phenylenediamine, 0.76 g (7.2mmol) of sodium carbonate and 150mL benzene, stirred rapidly for 3h at 85 . After completion of the reaction, the solvent was evaporated under reduced pressure and a small amount of water produced, and to obtain the final product was purified by column chromatography screen phenol separated.
With sodium carbonate In benzene at 85℃; for 3h; Inert atmosphere; II-5 Example II-5 Under nitrogen atmosphere, a 250ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel was added 20.23 g (85mmol) of 2,6-di-tert-butyl-4-mercaptophenol, 12.99 g (115mmol) 1,3-dichloropropane, 18.49 g (69mmol) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 0.76 g(7.2mmol) of sodium carbonate and 150mL of benzene, rapid stirring, the reaction at 85 deg. C for 3h. After completion of the reaction, the solvent was evaporated under reduced pressure and a small amount of water produced, purified by column chromatography to obtain the final product.
  • 14
  • [ 50-00-0 ]
  • [ 950-59-4 ]
  • [ 793-24-8 ]
  • [ 1831959-30-8 ]
YieldReaction ConditionsOperation in experiment
In benzene at 85℃; for 3h; Inert atmosphere; I-5 Example I-5 Example I-5 Under the protective atomosphere of nitrogen gas, to a 250ml four-necked flask equiped with a stirrer, a thermometer,a condensing tube and a dropping funnel, there were added 20.23g (85mmol) 2,6-di-tert-butyl-4-mercaptophenol,9.54g (115mmol) formaldehyde, 18.49g (69mmol) N- (1,3-dimethylbutyl)-N’-phenyl p-phenylene diamine and 150mLbenzene, rapidly stirred, reacted at 85 degrees Celsius for 3h. Upon completion of the reaction, the solvent and water(generated during the reaction) were removed by vacuum distillation, the titled hindered phenol compound was obtainedby using column chromatography. The compound was characterized as follows : 1H NMR (300MHz, CDCl3) : δ 0.80 (6H), 1.11-1.21 (4H), 1.36 (18H), 1.67 (2H), 3.47 (1 H), 4.80 (2H), 5.32 (1 H),6.80 (2H), 6.97 (5H), 7.17 (2H), 7.26 (2H), 7.55 (1 H); 13C NMR (75MHz, CDCl3) : δ 17.9, 22.4, 29.6, 34.6, 45.2, 52.7, 58.6, 119.4, 121.8, 126.2, 129.5, 131.2, 136.6,144.1, 146.1, 153.4; C33H46N2OS (calculated): : C 76.40, H 8.94, N 5.40, O 3.08, S 6.18; (measured): C 76.48, H 8.96, N 5.35, O 3.09,S 6.12.
In benzene at 85℃; for 3h; Inert atmosphere; I-5 Example I-5 Under nitrogen atmosphere, a 250ml four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel was added 20.23 g (85mmol) 2,6-di-(tert-butyl)-4-mercaptophenol, 9.54 g (115mmol )formaldehyde, 18.49 g (69mmol) N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and 150mL benzene rapidly stirred reaction at 85 deg. C for 3h. After completion of the reaction, the solvent was evaporated under reduced pressure and a small amount of water produced, purified by column chromatography to obtain the final product.
 

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