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Chemical Structure| 1835-49-0 Chemical Structure| 1835-49-0

Structure of 1835-49-0

Chemical Structure| 1835-49-0

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Product Details of [ 1835-49-0 ]

CAS No. :1835-49-0
Formula : C8F4N2
M.W : 200.09
SMILES Code : FC1=C(F)C(C#N)=C(F)C(F)=C1C#N
MDL No. :MFCD00001776
InChI Key :PCRSJGWFEMHHEW-UHFFFAOYSA-N
Pubchem ID :15783

Safety of [ 1835-49-0 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H301-H315-H319
Precautionary Statements:P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P310+P330-P405
Class:6.1
UN#:3439
Packing Group:

Computational Chemistry of [ 1835-49-0 ] Show Less

Physicochemical Properties

Num. heavy atoms 14
Num. arom. heavy atoms 6
Fraction Csp3 0.0
Num. rotatable bonds 0
Num. H-bond acceptors 6.0
Num. H-bond donors 0.0
Molar Refractivity 35.7
TPSA ?

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

47.58 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

1.12
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

1.76
Log Po/w (WLOGP)?

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

3.67
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.

2.46
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

3.51
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.5

Water Solubility

Log S (ESOL):?

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

-2.51
Solubility 0.623 mg/ml ; 0.00312 mol/l
Class?

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

Soluble
Log S (Ali)?

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

-2.38
Solubility 0.84 mg/ml ; 0.0042 mol/l
Class?

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

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

-3.69
Solubility 0.0407 mg/ml ; 0.000203 mol/l
Class?

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

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

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

No
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

No
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

No
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.

-6.27 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

0.0
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

0.0
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

1.0 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)

1.74

Application In Synthesis of [ 1835-49-0 ]

* 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 [ 1835-49-0 ]

[ 1835-49-0 ] Synthesis Path-Downstream   1~11

  • 1
  • [ 1835-49-0 ]
  • [ 75-16-1 ]
  • [ 5216-17-1 ]
  • [ 76437-39-3 ]
  • methyltrifluoroterephthalonitrile [ No CAS ]
  • 2
  • [ 1835-49-0 ]
  • [ 5216-17-1 ]
  • [ 76437-39-3 ]
  • methyltrifluoroterephthalonitrile [ No CAS ]
  • 3
  • [ 1897-41-2 ]
  • [ 1835-49-0 ]
YieldReaction ConditionsOperation in experiment
~ 90% With potassium fluoride; In N,N-dimethyl-formamide; at 110℃; for 10h;Product distribution / selectivity; About 8 g (about 0.03 mol) of <strong>[1897-41-2]1,4-dicyano-2,3,5,6-tetrachlorobenzene</strong> and about 8 g (about 0.137 mol) of KF were transferred into a flask containing about 60 mL of dry dimethyl formamide (DMF).The mixture was stirred at a temperature of about 110° C. for about ten hours. Nitrogen gas was used to blanket the mixture.The reaction mixture was poured into a beaker containing about 500 mL ice-water.The cooled mixture was then to collect the precipitate, which was washed by water and recrystallized with acetone.The recrystallized product, 1,4-dicyano-2,3,5,6-tetrafluorobenzene, was dried and measured to weigh about 5.4 g (about 90percent).The 19F NMR resonance of this product in CDCl3 was delta -128.8 (singlet).The reaction scheme (4) is illustrated below.
With potassium fluoride; C6H9BO4; In N,N-dimethyl-formamide; at 65℃; for 20h;Product distribution / selectivity; EXAMPLE 2710.5 g of commercially available <strong>[1897-41-2]tetrachloroterephthalonitrile</strong> are dispersed in 75 ml of DMF with 10 g of potassium fluoride KF. 3.1 g of the IB-4 complex are added to the suspension and the B/F ratio is 1/7. The suspension is stirred at 65° C. for 25 hours. The mixture is filtered, the solid is washed with twice 15 ml of DMF and the filtrate is precipitated from 1 L of water and separated by centrifugation. The product obtained is tetrafluoroterephthalonitrile which is 98percent pure as determined by NMR. The filtration residue is constituted of pure KCl, as determined by X-ray spectrometry. Under similar conditions, the <strong>[1897-41-2]tetrachloroterephthalonitrile</strong>+KF mixture shows no KCl X-ray line at 65° C. after 25 hours.
  • 4
  • [ 1835-49-0 ]
  • [ 5216-17-1 ]
YieldReaction ConditionsOperation in experiment
78%Chromat. With zeolite 4A; hydrogen;5%-palladium/activated carbon; In toluene; at 160℃; under 375.038 - 750.075 Torr; for 8h;autoclave;Conversion of starting material; Dry tetrafluoroterephthalonitrile 51.02 g (98% pure, 50.0 g in terms of tetrafluoroterephthalonitrile), dry 5% Pd/C 1.0 G, Zeolite 4A powder 37. 5 g (Molecular Sieve 4A produced by Union Showa K. K. ), and toluene 200.0 g were introduced into a 500 ml stainless steel autoclave (NU-4 model produced by Nitto Koatu Co., Ltd. ), and the autoclave was purged with nitrogen. Thereafter the contents were heated to 160C under stirring, and hydrogen pressurized at a pressure higher than that in the autoclave at the above temperature by 0.1 MPa was supplied to initiate hydrogenolysis. The rate of hydrogen absorption lowered in 2 hours after the hydrogen supply was initiated, so that the pressure in the autoclave was raised by 0. 05 MPa with hydrogen.The supply of hydrogen was terminated when the hydrogen absorption was achieved at 125 mol% (based on the mol of tetrafluoroterephthalonitrile under standard conditions). The above reaction was completed in 8 hours. Cooled to room temperature, the reaction slurry was filtered, and the filtrate was analyzed with the gas chromatography analyzer. The analysis gave a conversion of 98. 0% and a reaction yield of 78. 0% (product: 2,3, 5,6-tetrafluorobenzonitrile). The solvent of the above reaction solution was removed by means of an evaporator, and the residue was distilled under reduced pressure to obtain 2,3, 5, 6-tetrafluorobenzonitrile as a fraction under 50 mmHg at 88C.
20.7%Chromat. With hydrogen;5%-palladium/activated carbon; In water; toluene; at 160℃; under 750.075 Torr; for 3h;autoclave;Conversion of starting material; Reaction was conducted in the same manner as in Example 4 except that no zeolite was used. The results were that the hydrogenolysis reaction was completed in 3 hours and the hydrogen absorption was 42%. The analysis gave a conversion of 50. 4% and a reaction yield of 20. 7% (product: 2,3, 5,6-tetrafluorobenzonitrile).
24.1%Chromat. With hydrogen;5%-palladium/activated carbon; In toluene; at 160℃; under 375.038 - 750.075 Torr; for 4h;Conversion of starting material; Reaction was conducted in the same manner as in Example 1 except that no zeolite was used. The results were that the hydrogenolysis reaction was completed in 4 hours and the hydrogen absorption was 48%. The analysis gave a conversion of 55. 2% and a reaction yield of 24. 1% (product: 2,3, 5,6-tetrafluorobenzonitrile).
76 - 76.9%Chromat. With zeolite 4A; hydrogen;5%-palladium/activated carbon; In water; toluene; at 160℃; under 375.038 - 750.075 Torr; for 8 - 10h;autoclave;Conversion of starting material; Water-wet tetrafluoroterephthalonitrile 56.69 g (10% water content, 98% pure, 50.0 g in terms of tetrafluoroterephthalonitrile), water-wet 5% Pd/C 2.38 g (58% water content, 1.0 g in terms of Pd), and toluene 200.0 g were introduced into a 500 ml three-necked glass flask equipped with a stirrer, a thermometer, a Claisen tube and a cooling tube. The contents were heated to distill away toluene and water together in an amount of 150.2 g. After cooling, toluene 143.0 g was added and the water content was measured to be 150 ppm. The resultant reaction solution was introduced into a 500 ml stainless steel autoclave (NU-4 model produced by Nitto Koatu Co., Ltd. ), and further Zeolite 4A powder 37.5 g (Molecular Sieve 4A produced by Union Showa K. K. ) was added thereto. Then the autoclave was purged with nitrogen. THEREAFTER THE CONTENTS WERE HEATED TO 160C UNDER stirring, and hydrogen pressurized at a pressure higher than that in the autoclave at the above temperature by 0.1 MPa was supplied to initiate hydrogenolysis. The rate of hydrogen absorption lowered in 2 hours after the hydrogen supply was initiated, so that the pressure in the autoclave was raised BY 0. 05 MPa with hydrogen. The supply of hydrogen was terminated when the hydrogen absorption was achieved at 125 MOL% (based on the mol of tetrafluoroterephthalonitrile under standard conditions). The above reaction was completed in 8 hours. Cooled to room temperature, the reaction slurry was filtered, and the filtrate was analyzed with the gas chromatography analyzer. The analysis gave a conversion of 96.8% and a reaction yield of 76. 9% (product: 2,3, 5,6-tetrafluorobenzonitrile). Example 3 Reaction was conducted basically in the same manner as in Example 2 except that the amount of 5% Pd/C was reduced by half to 1.18 g (58% water content, 0.5 g in terms of Pd). The reaction was completed in 10 hours. The analysis gave a conversion of 96. 5% AND A reaction yield of 76. 0% (product: 2,3, 5,6-tetrafluorobenzonitrile).
84.4 - 89.1%Chromat. With zeolite 5A; hydrogen;5%-palladium/activated carbon; In water; toluene; at 160 - 180℃; under 750.075 Torr; for 5.16667 - 5.5h;autoclave;Conversion of starting material; Water-wet tetrafluoroterephthalonitrile 56. 69 G (10% water content, 98% pure, 50.0 g in terms of tetrafluoroterephthalonitrile), water-wet 5% Pd/C 1.18 g (58% water content, 0.5 g in terms of Pd), and toluene 200.0 g were introduced into a 500 ml three-necked glass flask equipped with a stirrer, a thermometer, a Claisen tube and a cooling tube. The contents were heated to distill away toluene and water together in an amount of 187.5 g. After cooling, toluene 187.5 g was added and the water content was measured to be 150 ppm. The resultant reaction solution was introduced into a 500 ml stainless steel autoclave (NU-4 model produced by Nitto Koatu Co., Ltd. ), and further Zeolite 5A powder 45 g (Molecular Sieve 5A produced by Union Showa K. K. ) was added thereto. Then the autoclave was purged with nitrogen. THEREAFTER THE CONTENTS WERE HEATED TO 160C under stirring, and hydrogen pressurized at a pressure higher than that in the autoclave at the above temperature by 0.1 MPa was supplied to initiate hydrogenolysis. The rate of hydrogen absorption lowered in approximately 5 hours and 30 minutes of reaction time, and the supply of hydrogen was terminated to end the reaction. The hydrogen absorption was 116 MOL% (based on the mol of tetrafluoroterephthalonitrile under standard conditions). Cooled to room temperature, the reaction slurry was filtered, and the filtrate was analyzed with the gas chromatography analyzer. The analysis gave a conversion of 97. 8% and a reaction yield of 84.4 % (product: 2,3, 5,6-tetrafluorobenzonitrile). Example 5 Reaction was conducted basically in the same manner as in Example 4 except that the amount of 5% Pd/C was altered to 2.38 g (58% water content, 1.0 g in terms of Pd) and that the amount of the Zeolite 5A powder was altered to 37.5 g (Molecular Sieve 5A produced by Union Showa K. K. ). The results were that the hydrogenolysis reaction was completed in 5 hours and 30 minutes and the hydrogen absorption was 114%. The analysis gave a conversion of 98. 2% and a reaction yield of 87. 5% (product: 2,3, 5, 6-tetrafluorobenzonitrile).Example 6 Reaction was conducted basically in the same manner as in Example 4 except that the amount of 5% Pd/C was altered to 1.43 g (58% water content, 0.6 g in terms of Pd). The results were that the hydrogenolysis reaction was completed in 5 hours and 20 minutes and the hydrogen absorption was 121%. The analysis gave a conversion of 99.4% and a reaction yield of 86. 2% (product: 2,3, 5, 6-tetrafluorobenzonitrile). Example 7 Reaction was conducted basically in the same manner as in Example 4 except that the hydrogenolysis temperature was altered to 170C. The results were that the hydrogenolysis reaction was completed in 5 hours and 30 minutes and the hydrogen absorption was 111%. The analysis gave a conversion of 99. 3% and a reaction yield of 87. 5% (product: 2,3, 5,6-tetrafluorobenzonitrile). Example 8 Reaction was conducted basically in the same manner as in Example 4 except that the hydrogenolysis temperature was altered to 180C. The results were that the hydrogenolysis reaction was completed in 5 hours and 10 minutes and the hydrogen absorption was 114%. The analysis gave a conversion of 99. 3% and a reaction yield of 89. 1% (product: 2,3, 5, 6-tetrafluorobenzonitrile). Example 9 Reaction was conducted basically in the same manner as in Example 4 except that the additional toluene was used in an amount of 147.5 g. The results were that the hydrogenolysis reaction was completed in 5 hours and 30 minutes and the hydrogen absorption was 112%. The analysis gave a conversion of 98. 9% and a reaction yield of 87. 0% (product: 2,3, 5,6-tetrafluorobenzonitrile). Example 10 Reaction was conducted basically in the same manner as in Example 4 except that the additional toluene was used in an amount of 107.5 g. The results were that the hydrogenolysis reaction was completed in 5 hours and 30 minutes and the hydrogen absorption was 108%. The analysis gave a conversion of 98.7% and a reaction yield of 86.5% (product: 2,3, 5,6-tetrafluorobenzonitrile).
34.7%Chromat. With hydrogen;5%-palladium/activated carbon; In water; toluene; at 160℃; under 750.075 Torr; for 5.5h;autoclave;Conversion of starting material; Reaction was conducted basically in the same manner as in Example 4 except that the zeolite was changed to Zeolite MS-13X. The results were that the hydrogenolysis reaction was completed in 5 hours and 30 minutes and the hydrogen absorption was 52%. The analysis gave a conversion of 69. 7% and a reaction yield of 34. 7% (product: 2,3, 5,6-tetrafluorobenzonitrile).

  • 5
  • [ 67-56-1 ]
  • [ 1835-49-0 ]
  • [ 327-54-8 ]
  • [ 5216-17-1 ]
  • [ 89992-52-9 ]
  • [ 3217-47-8 ]
YieldReaction ConditionsOperation in experiment
[Example 1]; In a conical flask, 20.6 g of 95% sulfuric acid was slowly added dropwise to 70 g (2.2 mol) of methanol with ice cooling. Then, into a 300-ml glass autoclave, the resulting sulfuric acid/methanol solution and a 5% Rh/C catalyst (available from NE Chemcat Corporation, hydrous product) in an amount of 0.25 g on a dry weight basis were charged. The system was purged with hydrogen to make a hydrogen pressure 0.1 MPa at room temperature. Heating of the autoclave and stirring of the contents in the EPO <DP n="20"/>autoclave were started, and the temperature was increased to 400C and was held constant for 1 hour. After the autoclave was cooled, 10 g (50 mmol) of tetrafluoroterephthalonitrile (available from Tokyo Kasei Kogyo Co., Ltd.) was fed to the autoclave, and the temperature was raised to 700C in a nitrogen atmosphere. At 700C, introduction of hydrogen was started. The reaction pressure was controlled so that the hydrogen absorption rate should become not more than 10 ml/min. After a lapse of 6 hours and 30 minutes, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 119% of the theoretical quantity of hydrogen absorbed. The reaction solution was filtered to separate the catalyst, and methanol was distilled off at atmospheric pressure. Thereafter, 100 g of water was added to the residue, and the mixture was refluxed by heating at an internal temperature of 1000C for 60 minutes. Then, methanol formed by hydrolysis of acetal was distilled off at atmospheric pressure. When the top temperature of the distillation reached 99C, the distillation was finished, and the resulting solution was cooled to room temperature. Then, the solution was extracted 3 times each with 30 g of toluene . EPO <DP n="21"/>From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below the detection limit, the amount of tetrafluoroterephthalaldehyde was 92.0 mol%, the amount of 2, 3, 5, 6-tetrafluorobenzene was 0.94 mol%, and the amount of 2, 3, 5, 6-tetrafluorobenzonitrile was 0.79 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of 3.39 mol% of 2, 3, 5, 6-tetrafluorobenzylamine was confirmed. The results are set forth in Table 1. [Example 2]The same operations as in Example 1 were carried out, except that as a catalyst a 5% Pd/C catalyst (available from NE Chemcat Corporation, hydrous product) was charged in an amount of 0.25 g on a dry weight basis. After a lapse of 3.3 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 117% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1.From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a EPO <DP n="22"/>result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below the detection limit, and the amount of tetrafluoroterephthalaldehyde was 68.9 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of14.8 mo1% of 2, 3, 5, 6-tetrafluorobenzylamine was confirmed.The results are set forth in Table 1. [Example 2]; The same operations as in Example 1 were carried out, except that as a catalyst a 5% Pd/C catalyst (available from NE Chemcat Corporation, hydrous product) was charged in an amount of 0.25 g on a dry weight basis. After a lapse of 3.3 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 117% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1.From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a EPO <DP n="22"/>result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below the detection limit, and the amount of tetrafluoroterephthalaldehyde was 68.9 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of14.8 mo1% of 2, 3, 5, 6-tetrafluorobenzylamine was confirmed.The results are set forth in Table 1.; [Example 3] The same operations as in Example 1 were carried out, except that the temperature of the pretreatment of the catalyst with hydrogen was changed from 400C to 500C.After a lapse of 5.5 hours, absorption of hydrogen ceased.The quantity of hydrogen absorbed was 106% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1.From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was ...
[Example 7]; The same operations as in Example 1 were carried out, except that the catalyst used was changed from the 5% Rh/C catalyst (available from NE Chemcat Corporation, hydrous product) to a 2% Rh/C catalyst (available from NE Chemcat EPO <DP n="26"/>Corporation, hydrous product) . After a lapse of 7.3 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 114% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1.From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below the detection limit, the amount of tetrafluoroterephthalaldehyde was 88.6 mol%, the amount of 2, 3, 5, 6-tetrafluorobenzene was 1.15 mol%, and the amount of 2, 3, 5, 6-tetrafluorobenzonitrile was 2.63 ralphaol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of 2.36 mol% of 2, 3, 5, 6-tetrafluorobenzylamine was confirmed. The results are set forth in Table 1.
  • 6
  • [ 67-56-1 ]
  • [ 1835-49-0 ]
  • 4-cyano-2,3,5,6-tetrafluorobenzaldehyde [ No CAS ]
  • [ 327-54-8 ]
  • [ 5216-17-1 ]
  • [ 89992-52-9 ]
  • [ 3217-47-8 ]
YieldReaction ConditionsOperation in experiment
[Comparative Example 1]; The same operations as in Example 1 were carried out, except that the amount of the catalyst used was changed from 0.25 g to 0.05 g on a dry weight basis. After a lapse of 7.0 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 83% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1. EPO <DP n="28"/>From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, the tetrafluoroterephthalonitrile as a raw material remained in an amount of 21.0 mol%, and tetrafluoroterephthalaldehyde was obtained in an amount of only 5.0 mol%. The amount of 2, 3, 5, 6-tetrafluorobenzene was 0.65 mol%, the amount of 2,3,5,6- tetrafluorobenzonitrile was 0.53 mol%, and 1-cyano- 2, 3, 5, 6-tetrafluorobenzaldehyde wherein a nitrile group on only one side had reacted was obtained in an amount of 63.1 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of 2.88 mol% of 2,3,5,6- tetrafluorobenzylamine was confirmed. The results are set forth in Table 2.; [Comparative Example 3]; The same operations as in Example 1 were carried out, except that the amount of sulfuric acid used was changed from 20.6 g to 5.15 g (50 mmol). After a lapse of 4.2 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 47% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1.From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below EPO <DP n="30"/>the detection limit, and tetrafluoroterephthalaldehyde was obtained in an amount of only 14.5 mol%. The amount of 2, 3, 5, 6-tetrafluorobenzene was 0.81 mol%, the amount of 2, 3, 5, 6-tetrafluorobenzonitrile was 0.67 mol%, and 1- cyano-2, 3, 5, 6-tetrafluorobenzaldehyde wherein a nitrile group on only one side had reacted was obtained in an amount of 54.0 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, presence of 0.04 mol% of 2,3,5,6- tetrafluorobenzylamine was confirmed. The results are set forth in Table 2.
  • 7
  • [ 67-56-1 ]
  • [ 1835-49-0 ]
  • 4-cyano-2,3,5,6-tetrafluorobenzaldehyde [ No CAS ]
  • [ 327-54-8 ]
  • [ 5216-17-1 ]
  • [ 3217-47-8 ]
YieldReaction ConditionsOperation in experiment
[Comparative Example 4]; The same operations as in Example 1 were carried out, except that the reaction temperature was changed from 7O0C to 12O0C. After a lapse of 8.0 hours, absorption of hydrogen ceased. The quantity of hydrogen absorbed was 103% of the theoretical quantity of hydrogen absorbed. Treatment of the reaction solution was carried out in the same manner as in Example 1. From the toluene extract, a small amount of a sample was withdrawn, and it was subjected to GC analysis. As a result of the analysis, a peak of the tetrafluoroterephthalonitrile as a raw material was below the detection limit, and tetrafluoroterephthalaldehyde was EPO <DP n="31"/>obtained in an amount of only 2.6 mol%. The amount of 2, 3, 5, beta-tetrafluorobenzene was 1.08 mol%, the amount of 2, 3, 5, 6-tetrafluorobenzonitrile was 0.87 mol%, and 1- cyano-2, 3, 5, 6-tetrafluorobenzaldehyde wherein a nitrile group on only one side had reacted was obtained in an amount of 42.2 mol%. On the other hand, the aqueous phase was neutralized and then subjected to GC analysis. As a result of the analysis, the amount of 2,3,5,6- tetrafluorobenzylamine was below the detection limit. The results are set forth in Table 2.
  • 9
  • [ 56525-79-2 ]
  • [ 1835-49-0 ]
  • 1,4-dicyano-2,3,5,6-tetrakis(3,6-diphenylcarbazol-9-yl)benzene [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% 480 mg (12.0 mmol) of 60percent sodium hydride was rinsed with hexane, and then added to a dried THF solution of 3.20 g (10.0 mmol) of <strong>[56525-79-2]3,6-diphenylcarbazole</strong>, which was being stirred under a nitrogen atmosphere, at room temperature. After stirring for 30 minutes, 400 mg (2.00 mmol) of tetrafluoroterephthalonitrile was added to the mixture, and the mixture was stirred under a nitrogen atmonphere at room temperature for 10 hours. Thereafter, the reaction was terminated with 5 mE of water, and the mixture was concentrated under reduced pressure to provide a yellow solid matter. The resulting solid matter was purified by silica gel chromatography with chloroform as a developing solvent, thereby providing an orange powdered solid matter in a yield amount of 2.20 g and a yield of 79percent.
  • 10
  • [ 1835-49-0 ]
  • [ 79802-71-4 ]
  • C46H16F8N8 [ No CAS ]
  • 11
  • [ 784-04-3 ]
  • [ 1835-49-0 ]
  • 2C16H12O*C8F4N2 [ No CAS ]
 

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