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Chemical Structure| 29651-54-5

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Product Details of [ 29651-54-5 ]

CAS No. :29651-54-5
Formula : C24H32O2
M.W : 352.51
SMILES Code : OC1=CC=C(C2(C3=CC=C(O)C=C3)CCCCCCCCCCC2)C=C1
MDL No. :MFCD28369391
InChI Key :BHWMWBACMSEDTE-UHFFFAOYSA-N
Pubchem ID :15850060

Safety of [ 29651-54-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 29651-54-5 ] Show Less

Physicochemical Properties

Num. heavy atoms 26
Num. arom. heavy atoms 12
Fraction Csp3 0.5
Num. rotatable bonds 2
Num. H-bond acceptors 2.0
Num. H-bond donors 2.0
Molar Refractivity 110.59
TPSA ?

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

40.46 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

3.4
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

8.67
Log Po/w (WLOGP)?

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

6.69
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.

4.87
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

5.6
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

5.85

Water Solubility

Log S (ESOL):?

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

-7.7
Solubility 0.00000708 mg/ml ; 0.0000000201 mol/l
Class?

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

Poorly soluble
Log S (Ali)?

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

-9.4
Solubility 0.000000141 mg/ml ; 0.0000000004 mol/l
Class?

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

Poorly 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

-7.05
Solubility 0.0000313 mg/ml ; 0.0000000887 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

No
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

No
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

No
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.

-2.29 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

1.0
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.

0.0 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<2.0
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)

3.04

Application In Synthesis of [ 29651-54-5 ]

* 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 [ 29651-54-5 ]

[ 29651-54-5 ] Synthesis Path-Downstream   1~6

  • 1
  • [ 29651-54-5 ]
  • [ 358-23-6 ]
  • [ 632336-53-9 ]
  • 2
  • [ 830-13-7 ]
  • [ 108-95-2 ]
  • [ 29651-54-5 ]
YieldReaction ConditionsOperation in experiment
75.4% In a 500 ml glass reaction vessel,258.14 g (2.74 mol) of phenol,And 13.73 g (0.137 mol) of 98% sulfuric acid were charged,The temperature was raised to 80 C. After stirring at the same temperature for 1 hour,It was cooled to 60 C.,50.02 g (0.274 mol) of cyclododecanone,5.57 g (0.0275 mol) of n-dodecylmercaptan was charged and stirred for 8 hours at 64 to 68 C. under reduced pressure of 2.7 kPa while blowing nitrogen gas. After completion of stirring, the mixture was allowed to stand still overnight,When the reaction mass was analyzed by gas chromatography,No cyclododecanone was detected. To the resulting reaction mass were added toluene,Ion exchanged water was added and neutralized with sodium hydroxide,Ion exchangeIt was washed with water. The obtained organic layer was cooled as it was,Precipitated crystals were taken out by filtration. The obtained crystals were recrystallized from methanol water, taken out by filtration,After drying, 72.89 g of 1,1-bis (4-hydroxyphenyl) cyclododecane was obtained (HPLC purity 100%, yield 75.4%).
77.04 g 258.19 g (2.74 mol) of phenol and 13.72 g (0.137 mol) of 98% sulfuric acid were charged into a 500 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 80 C. After stirring at the same temperature for 1 hour, 50.09 g (0.275 mol) of cyclododecanone at 60 C.,5.54 g (0.0274 mol) of n-dodecylmercaptan was added and reacted at 65 C. while removing water at 1.3 kPa until the remaining amount of cyclododecanone reached 50% of the initial charge amount.After recovering pressure to normal pressure with nitrogen gas, it was cooled to 30 C. and left to stand at the same temperature for 52 hours.0.15 g of the solidified reaction mass was scraped off, and the reaction mass was analyzed by gas chromatography. As a result, the remaining amount of cyclododecanone was 1% of the initially charged amount, and 1, 1-bis (4-hydroxy Phenyl) cyclododecane (the molar ratio to the initially charged amount of cyclododecanone) was 90.2%. Toluene and ion exchanged water were added to the obtained reaction mass, neutralized with sodium hydroxide, and then washed with ion exchanged water. The obtained organic layer was cooled as it was, the precipitated crystal was taken out by filtration and dried. The obtained crystals were recrystallized from methanol water, taken out by filtration and dried to obtain 77.04 g (0.219 mol, yield 79.5 mmol) of 1, 1-bis (4-hydroxyphenyl) cyclododecane %, HPLC purity 100%) was obtained
YieldReaction ConditionsOperation in experiment
Illustrative non-limiting examples of non-phosphorus dihydroxyaromatic compounds include: 2,2-bis(4-hydroxyphenyl-propane (bisphenol A); ... 1,1-bis(4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxyphenyl)decane; 1,4-bis(4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclododecane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; ...
The following dihydroxyaromatic compounds are illustrative: ... 2-(4-Hydroxyphenyl)-2-3-hydroxyphenyl) propane 2,2-Bis(4-hydroxyphenyl)butane 1,1-Bis(4-hydroxyphenyl)isobutane 1,1-Bis(4-hydroxyphenyl)cyclohexane 1,1-Bis(4-hydroxyphenyl)cyclododecane Trans-2,3-bis(4-hydroxyphenyl)-2-butene 2,2-Bis(4-hydroxyphenyl)adamantane alpha,alpha'-Bis(4-hydroxyphenyl)toluene ...
The following dihydroxyaromatic compounds are illustrative: ... 2-(4-Hydroxyphenyl)-2-(3-hydroxyphenyl) propane 2,2-Bis(4-hydroxyphenyl)butane 1,1-Bis(4-hydroxyphenyl)isobutane 1,1-Bis(4-hydroxyphenyl)cyclohexane 1,1-Bis(4-hydroxyphenyl)cyclododecane Trans-2,3-bis(4-hydroxyphenyl)-2-butene 2,2-Bis(4-hydroxyphenyl)adamantane alpha,alpha'-Bis(4-hydroxyphenyl)toluene ...
The A1 values may be considered as being derived from dihydroxyaromatic compounds of the formula HO--A1 --OH, preferably bisphenols of the formula HO--A2 --Y--A3 --OH. The following dihydroxy compounds are illustrative: ... 2-(4-Hydroxyphenyl)-2-(3-hydroxyphenyl) propane 2,2-Bis(4-hydroxyphenyl)butane 1,1-Bis(4-hydroxyphenyl)isobutane 1,1-Bis(4-hydroxyphenyl)cyclohexane 1,1-Bis(4-hydroxyphenyl)cyclododecane Trans-2,3-bis(4-hydroxyphenyl)-2-butene 2,2-Bis(4-hydroxyphenyl)adamantane alpha,alpha'-Bis(4-hydroxyphenyl)toluene ...
...ay be considered as being derived from dihydroxy compounds of the formula HO--R4 --OH, especially dihydroxyaromatic compounds and preferably bisphenols of the formula HO--A2 --Y3 --A3 --OH. The following dihydroxy compounds are illustrative: Ethylene glycol ... 2-(4-Hydroxyphenyl)-2-(3-hydroxyphenyl) propane 2,2-Bis(4-hydroxyphenyl)butane 1,1-Bis(4-hydroxyphenyl)isobutane 1,1-Bis(4-hydroxyphenyl)cyclohexane 1,1-Bis(4-hydroxyphenyl)cyclododecane Trans-2,3-bis(4-hydroxyphenyl)-2-butene 2,2-Bis(4-hydroxyphenyl)adamantane alpha,alpha'-Bis(4-hydroxyphenyl)toluene ...

  • 4
  • [ 29651-54-5 ]
  • [ 506-68-3 ]
  • [ 1187462-93-6 ]
YieldReaction ConditionsOperation in experiment
With triethylamine; In acetone; at -5 - 0℃; for 2.18333h;Inert atmosphere of nitrogen; Example 1Synthesis of U-Bis(4-cyanatophenyl)cyclododecane[0083] A 250 milliliter, three neck, glass, round bottom reactor was charged with 1,1- bis(4-hydroxyphenyl)cyclododecane (17.63 grams, 0.10 hydroxyl equivalent) and acetone (125 milliliters, 7.09 milliliter per gram of bisphenol). The reactor was additionally equipped with a condenser (maintained at O0C), a thermometer, an overhead nitrogen inlet (1 LPM N2 used), and magnetic stirring. Stirring commenced to give a solution at 21.5C. Cyanogen bromide (11.12 grams, 0.105 mole, 1.05:1 cyanogen bromide:hydroxyl equivalent ratio) was added to the solution and immediately dissolved therein. A dry ice- acetone bath for cooling was placed under the reactor followed cooling and equilibration of the stirred solution at -50C. Triethylamine (10.17 grams, 0.1005 mole, 1.005 triethylamine:hydroxyl equivalent ratio) was added using a syringe in aliquots that maintained the reaction temperature at -5 to O0C. The total addition time for the triethylamine was 30 minutes. Addition of the initial aliquot of triethylamine induced haziness in the stirred solution with further additions inducing formation of a white slurry of triethylamine hydrobromide. <n="24"/>[0084] After 8 minutes of post-reaction at -5 to 0.5C, high pressure liquid chromatographic (HPLC) analysis of a sample of the reaction product revealed the presence of 0.68 area percent unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 4.43 area % monocyanate, and 93.98 area % dicyanate, with the balance as 7 minor peaks. After a cumulative 45 minutes of postreaction at -5C to O0C, HPLC analysis of a sample of the reaction product revealed the presence of 0.84 area percent unreacted cyclododecane bisphenol, 5.34 area % monocyanate, and 93.51 area % dicyanate, with the balance as one minor peak.[0085] After a cumulative 101 minutes of post-reaction, the product slurry was added to a beaker of magnetically stirred deionized water (1.5 liters) providing an aqueous slurry. After 5 minutes of stirring, gravity filtration of the aqueous slurry through filter paper recovered the white powder product. The product from the filter paper was rinsed into a beaker using deionized water to a total volume of 200 milliliters, followed by the addition of dichloromethane (200 milliliters). A solution formed in the dichloromethane layer. The mixture was added to a separatory funnel, thoroughly mixed, allowed to settle, and then the dichloromethane layer recovered, with the aqueous layer discarded to waste. The dichloromethane solution was added back into the separatory funnel and extracted with fresh deionized water (200 milliliters) two additional times.[0086] The resultant hazy dichloromethane solution was dried over granular anhydrous sodium sulfate (5 grams) to give a clear solution which was then passed through a bed of anhydrous sodium sulfate (25 grams) supported on a 60 milliliter, medium fritted glass funnel attached to a side arm vacuum flask. The clear filtrate was rotary evaporated using a maximum oil bath temperature of 50C until the vacuum was <3.5 mm Hg. A total of 19.81 grams (98.43 % unconnected, isolated yield) of white, crystalline product was recovered. HPLC analysis of a sample of the product revealed the presence of 0.47 area percent unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 3.09 area % monocyanate, and 96.44 area % dicyanate.; Example 3Synthesis and Recrystallization to Produce High Purity U-Bis(4- cyanatophenyPcyclododecane[0088] The synthesis of l,l-bis(4-cyanatophenyl)cyclododecane of Example 1 was repeated, but with a 2-fold increase in scale. The 38.86 grams of recovered product assayed 0.69 area percent unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 3.91 area % monocyanate, and 95.40 area % dicyanate by HPLC analysis. Recrystallization was performed by forming a solution in boiling acetone (50 milliliters), then holding for 24 hours at 230C. The acetone solution was removed from the crystalline product via decantation. HPLC analysis of a portion of the damp crystalline product revealed the presence of no detectable unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 1.02 area % monocyanate, and 98.98 area % dicyanate. A second recrystallization of the damp crystalline product from acetone (40 milliliters) followed by drying in the vacuum oven at 50C for 48 hours provided 20.12 grams of brilliant white product with no detectable unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 0.42 area % monocyanate, and 99.58 area % dicyanate by HPLC analysis. Combination of the acetone solution decants from the two recrystallizations followed by concentration of the solution to a volume of 28 milliliters yielded a second crop of brilliant white product (8.39 grams) with a trace (non-integratable) of unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 2.28 area % monocyanate, and 97.72 area % dicyanate by HPLC analysis.
With triethylamine; In acetone; at -5 - 0℃; for 2.18333h;Inert atmosphere of nitrogen; Reference Example 1Synthesis of U-Bis(4-cvanatophenyl)cvclododecane[0126] A 250 milliliter, three neck, glass, round bottom reactor was charged with 1,1- bis(4-hydroxyphenyl)cyclododecane (17.63 grams, 0.10 hydroxyl equivalent) and acetone (125 milliliters, 7.09 milliliter per gram of bisphenol). The reactor was additionally equipped with a condenser (maintained at O0C), a thermometer, an overhead nitrogen inlet (1 LPM N2 used), and magnetic stirring. Stirring commenced to give a solution at 21.5C. Cyanogen bromide (11.12 grams, 0.105 mole, 1.05:1 cyanogen bromide:hydroxyl equivalent ratio) was added to the solution and immediately dissolved therein. A dry ice- acetone bath for cooling was placed under the reactor followed cooling and equilibration of the stirred solution at -50C. Triethylamine (10.17 grams, 0.1005 mole, 1.005 triethylamine : hydroxyl equivalent ratio) was added using a syringe in aliquots that maintained the reaction temperature at -5 to O0C. The total addition time for the triethylamine was 30 minutes. Addition of the initial aliquot of triethylamine induced haziness in the stirred solution with further additions inducing formation of a white slurry of triethylamine hydrobromide. [0127] After 8 minutes of post-reaction at -5 to 0.5C high pressure liquid chromatographic (HPLC) analysis of a sample of the reaction product revealed the presence of 0.68 area percent unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 4.43 area % monocyanate and 93.98 area % dicyanate with the balance as 7 minor peaks. After a cumulative 45 minutes of postreaction at -5 to O0C HPLC analysis of a sample of the reaction product revealed the presence of 0.84 area percent unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 5.34 area % monocyanate and 93.51 area % dicyanate with the balance as one minor peak.[0128] After a cumulative 101 minutes of post-reaction, the product slurry was added to a beaker of magnetically stirred deionized water (1.5 liters) providing an aqueous slurry. After 5 minutes of stirring, gravity filtration of the aqueous slurry through filter paper <n="41"/>recovered the white powder product. The product from the filter paper was rinsed into a beaker using deionized water to a total volume of 200 milliliters, followed by the addition of dichloromethane (200 milliliters). A solution formed in the dichloromethane layer. The mixture was added to a separatory funnel, thoroughly mixed, allowed to settle, and then the dichloromethane layer recovered, with the aqueous layer discarded to waste. The dichloromethane solution was added back into the separatory funnel and extracted with fresh deionized water (200 milliliters) two additional times.[0129] The resultant hazy dichloromethane solution was dried over granular anhydrous sodium sulfate (5 grams) to give a clear solution which was then passed through a bed of anhydrous sodium sulfate (25 grams) supported on a 60 milliliter, medium fritted glass funnel attached to a side arm vacuum flask. The clear filtrate was rotary evaporated using a maximum oil bath temperature of 50C until the vacuum was <3.5 mm Hg. A total of 19.81 grams (98.43 % unconnected, isolated yield) of white, crystalline product was recovered. HPLC analysis of a sample of the product revealed the presence of 0.47 area percent unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 3.09 area % monocyanate and 96.44 area % dicyanate.; Reference Example 2Synthesis and Recrystallization to Produce High Purity U-Bis(4- cyanatophenyPcyclododecane[0130] The synthesis of dicyanate of l,l-bis(4-hydroxyphenyl)cyclododecane ofReference Example 1 was repeated, but with a 2-fold increase in scale. The 38.86 grams of recovered product assayed 0.69 area percent unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 3.91 area % monocyanate and 95.40 area % dicyanate by HPLC analysis. Recrystallization was performed by forming a solution in boiling acetone (50 milliliters), then holding for 24 hours at 23C. The acetone solution was removed from the crystalline product via decantation. HPLC analysis of a portion of the damp crystalline product revealed the presence of no detectable unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 1.02 area % monocyanate and 98.98 area % dicyanate. A second recrystallization of the damp crystalline product from acetone (40 milliliters) followed by drying in the vacuum oven at 50C for 48 hours provided 20.12 grams of <n="42"/>brilliant white product with no detectable unreacted l,l-bis(4- hydroxyphenyl)cyclododecane, 0.42 area % monocyanate and 99.58 area % dicyanate by HPLC analysis. Combination of the acetone solution decants from the two recrystallizations followed by concentration of the solution to a volume of 28 milliliters yielded a second crop of brilliant white product (8.39 grams) with a trace (non-integratable) of unreacted l,l-bis(4-hydroxyphenyl)cyclododecane, 2.28 area % monocyanate and 97.72 area % dicyanate by HPLC analysis.
  • 5
  • [ 29651-54-5 ]
  • [ 35466-83-2 ]
  • [ 15022-08-9 ]
  • [ 1187462-94-7 ]
YieldReaction ConditionsOperation in experiment
With triphenylphosphine;5%-palladium/activated carbon; at 77.5 - 80℃; for 10.1167h; Allyl alcohol (101.58 grams, 1.75 moles), dimethyl carbonate (157.55 grams, 1.75 moles) and sodium methoxide catalyst (0.18 gram, 0.065 percent by weight) were added to a 500 milliliter, 3 neck, round bottom glass reactor and maintained at room temperature (23C) with stirring under a nitrogen atmosphere. The reactor was additionally outfitted with a chilled condenser, a thermometer, magnetic stirring, and a thermostatically controlled heating mantle. An equilibrium mixture of allylmethyl carbonate, diallyl carbonate and methanol was rapidly formed concurrent with cooling of the reactor contents to 15.5C. After 13 minutes l,l-bis(4-hydroxyphenyl)cyclododecane (28.31 grams, 0.1606 equivalent of hydroxy groups) was added to the reactor, followed by a mixture of triphenylphosphine (0.56 gram, 0.204 percent by weight) and 5% palladium on carbon (0.38 gram, 0.127 percent by weight). The l,l-bis(4-hydroxyphenyl)cyclododecane assayed 99.76 area % via high pressure liquid chromatographic (HPLC) analysis with the balance consisting of 2 minor components (0.09 and 0.15 area %). Heating commenced and over the next 127 minutes the reaction temperature reached 79 - 800C. The reaction mixture was maintained <n="37"/>for 8 hours at 77.5 - 800C and then cooled to room temperature and vacuum filtered through a bed of diatomaceous earth packed on a medium fritted glass funnel. The recovered filtrate was rotary evaporated at a maximum oil bath temperature of 1000C and to a vacuum of 1.7 mm Hg pressure to provide a transparent, light yellow colored, liquid (35.04 grams) which became a tacky solid at room temperature.[0119] HPLC analysis revealed the presence of 96.78 area % allyl ether of l,l-bis(4- hydroxyphenyl)cyclododecane with the balance as a single minor component (3.22 area %). The single minor component was removed by dissolving the product in dichloromethane (100 milliliters) and passing the resultant solution through a 2 inch deep by 1.75 inch diameter bed of silica gel (230-400 mesh particle size, 60 angstrom mean pore size, 550 m2/gram surface dimension) supported on a medium fritted glass funnel. After elution from the silica gel bed with additional dichloromethane, a yellow band remained in the region of the origin. Rotary evaporation provided 33.98 grams (98.94 % isolated yield) of pale yellow colored tacky solid.[0120] HPLC analysis revealed the presence of 99.57 area % allyl ether of l,l-bis(4- hydroxyphenyl)cyclododecane with the balance as 2 minor components (0.22 and 0.21 area %). Infrared spectrophotometric analysis of a film sample of the product on a KBr plate revealed peaks in the range expected for unsaturated C-H stretch (3032, 3058, 3081 cm" 1X saturated C-H stretch (2862, 2934 cm"1 [shoulder present on both]), C=C stretch (1581, 1607 cm"1), C-O stretch (1026 cm"1), and CH=CH2 deformation (924, 998 cm"1), accompanied by total absence of hydroxyl group absorbance thus confirming full conversion of the phenolic hydroxyl groups to allyl ether groups.
  • 6
  • [ 29651-54-5 ]
  • [ 31643-49-9 ]
  • C40H36N4O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate; In N,N-dimethyl-formamide; at 20 - 85℃; The compound of the following formula (C) was synthesized in the following manner.42.6 g of 1,1-bis (4'-hydroxyphenyl) -cyclododecane and 150 mL of dimethylformamide were placed in a 500 mL flask (3 mL) Neck round bottom flask) and stirred at room temperature.After stirring, 41.9 g of 4-nitrophthalonitrile was further added, and 50 g of DMF was added and dissolved by stirring.50.2 g of potassium carbonate was added together with 50 g of DMF, and the temperature was raised to 85 DEG C with stirring.After cooling to room temperature, the cooled reaction solution was neutralized and precipitated by pouring into a 0.2N hydrochloric acid aqueous solution. The precipitate was filtered and washed with water.The filtered product was dried in a vacuum oven at 100 for one day to remove water and residual solvent to obtain the target product.NMR analysis of the target product was carried out using an apparatus (Agilent 500 MHz NMR device) (solvent: DMSO (d6)) and the result is shown in FIG.
 

Historical Records

Technical Information

Categories

Related Functional Groups of
[ 29651-54-5 ]

Aryls

Chemical Structure| 77-40-7

A203830 [77-40-7]

4,4'-(Butane-2,2-diyl)diphenol

Similarity: 1.00

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