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Chemical Structure| 5216-17-1 Chemical Structure| 5216-17-1

Structure of 5216-17-1

Chemical Structure| 5216-17-1

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Product Details of [ 5216-17-1 ]

CAS No. :5216-17-1
Formula : C7HF4N
M.W : 175.08
SMILES Code : N#CC1=C(F)C(F)=CC(F)=C1F
MDL No. :MFCD00012286
InChI Key :IOQMWOBRUDNEOA-UHFFFAOYSA-N
Pubchem ID :297546

Safety of [ 5216-17-1 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H302-H311-H315-H319-H332
Precautionary Statements:P261-P280-P305+P351+P338-P310
Class:6.1
UN#:3439
Packing Group:

Computational Chemistry of [ 5216-17-1 ] Show Less

Physicochemical Properties

Num. heavy atoms 12
Num. arom. heavy atoms 6
Fraction Csp3 0.0
Num. rotatable bonds 0
Num. H-bond acceptors 5.0
Num. H-bond donors 0.0
Molar Refractivity 30.99
TPSA ?

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

23.79 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

1.52
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

2.15
Log Po/w (WLOGP)?

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

3.8
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.

3.17
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

3.5
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.83

Water Solubility

Log S (ESOL):?

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

-2.65
Solubility 0.392 mg/ml ; 0.00224 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.

-2.28
Solubility 0.915 mg/ml ; 0.00523 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

-3.6
Solubility 0.0443 mg/ml ; 0.000253 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.

-5.84 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

2.0
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)

1.69

Application In Synthesis of [ 5216-17-1 ]

* 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 [ 5216-17-1 ]

[ 5216-17-1 ] Synthesis Path-Downstream   1~35

  • 3
  • [ 1835-49-0 ]
  • [ 75-16-1 ]
  • [ 5216-17-1 ]
  • [ 76437-39-3 ]
  • methyltrifluoroterephthalonitrile [ No CAS ]
  • 4
  • [ 1835-49-0 ]
  • [ 5216-17-1 ]
  • [ 76437-39-3 ]
  • methyltrifluoroterephthalonitrile [ No CAS ]
  • 7
  • [ 773-82-0 ]
  • [ 4084-38-2 ]
  • [ 64248-63-1 ]
  • [ 5216-17-1 ]
  • [ 241154-09-6 ]
YieldReaction ConditionsOperation in experiment
100% Example 3 (Hydrodecyanation Reaction) A reaction was carried out in the same way as in Example 1, except that 1.0 g of triethylamine was added as a co-catalyst and the reaction time was made 7 hours. The conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 100% and the yield of 2,3,5,6-tetrafluorobenzonitrile was 77%.
100% Example 4 (Hydrodecyanation Reaction) By a method similar to Example 1 and using 125 g of diethyleneglycol dimethyl ether and 1.60 g of 5% palladium/activated carbon, a reaction was carried out at 100 C. for 1.5 hours. The conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 100% and the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 37%.
99% Example 7 (Hydrodecyanation Reaction) 115 g of toluene, 1.60 g of 5% palladium/activated carbon, 1.20 g of formic acid, and 1.0 g of 2,3,5,6-tetrafluoroterephthalonitrile were added to a 500 cc stainless steel autoclave equipped with a Teflon inner tube in a nitrogen atmosphere. The gas phase was sufficiently replaced with hydrogen gas, then the autoclave was sealed and heated to 150 C. After 2 hours, the reaction solution was analyzed by gas chromatography, whereupon the conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 99% and the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 63%.
98% Example 1 (Hydrodecyanation Reaction) 100 g of toluene, 0.20 g of 5% palladium/activated carbon, and 1.0 g of 2,3,5,6-tetrafluoroterephthalonitrile were added to a 500 cc glass three-necked flask with a reflux condenser in a nitrogen atmosphere. The gas phase was sufficiently substituted by hydrogen gas, then a hydrogen balloon was attached to the top portion of the reflux condenser and the resulting mixture was heated to 100 C. After 8 hours reaction, the reaction solution was analyzed by gas chromatography, whereupon the rate of conversion of 2,3,5,6-tetrafluorotetraphthalonitrile was found to be 98%, the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 73%.
95% Example 6 (Hydrodecyanation Reaction) By a method similar to Example 1 and using 100 g of toluene, 1.00 g of 5% palladium/activated carbon, 0.70 g of ethylenediaminetetraacetic acid, and 5.0 g of 2,3,5,6-tetrafluoroterephthalonitrile, a reaction was carried out at 100 C. for 22 hours. The conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 95% and the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 81%.
89% Example 5 (Hydrodecyanation Reaction) A reaction was carried out in the same way as in Example 4, except that 100 g of 2-propanol was used as the solvent and the reaction time was made 3 hours. The conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 89% and the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 38%.
82% Example 2 (Hydrodecyanation Reaction) Using a method similar to Example 1 and using 75 g of formic acid, 5.0 g of Raney nickel, and 2.5 g of 2,3,5,6-tetrafluoroterephthalonitrile, a reaction was carried out at 80 C. for 30 minutes. The conversion of 2,3,5,6-tetrafluoroterephthalonitrile was found to be 82% and the yield of 2,3,5,6-tetrafluorobenzonitrile (based on 2,3,5,6-tetrafluoroterephthalonitrile) was 35%.

  • 10
  • [ 5216-17-1 ]
  • [ 89992-52-9 ]
  • 11
  • [ 5216-17-1 ]
  • N-(4'-sulfamoylbenzoyl)-2,3,5,6-tetrafluorobenzylamine [ No CAS ]
  • 12
  • [ 67-56-1 ]
  • [ 5216-17-1 ]
  • [ 306739-71-9 ]
  • 14
  • [ 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).

YieldReaction ConditionsOperation in experiment
99.9% EXAMPLE 5 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 4 was performed except for changing the temperature at the stirring in a hydrogen atmosphere to 10 C. After the distillation, 101.43 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 78.4%).
99.9% EXAMPLE 10 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 9 was performed except for using 1.74 g of stannous sulfate and 12.39 g of sponge nickel having a water content of 6.96 g, and changing the time at the stirring in a hydrogen atmosphere to 7 hours. Before the distillation, the main products of the reaction solution were 2,3,5,6-tetrafluorobenzaldehyde and 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal. After the distillation, 109.33 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 84.6 %).
99.9% EXAMPLE 11 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 9 was performed except for using 1.15 g of zinc sulfate and 8.26 g of sponge nickel having a water content of 6.31 g, and changing the time at the stirring in a hydrogen atmosphere to 7.5 hours. Before the distillation, the main products of the reaction solution were 2,3,5,6-tetrafluorobenzaldehyde and 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal. After the distillation, 106.31 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 82.2 %).
99.9% EXAMPLE 6 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 4 was performed except for changing the temperature at the stirring in a hydrogen atmosphere to 30 C. After the distillation, 101.47 g of 2.3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 78.4%).
99.9% EXAMPLE 7 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 3 was performed except for using 9.33 g of sponge nickel having a water content of 6.83 g. Before the distillation, the main products of the reaction solution were 2,3,5,6-tetrafluorobenzaldehyde and 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal. After the distillation, 104.29 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 80.6%).
99.9% EXAMPLE 9 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde The same operation as in Example 3 was performed except for using a catalyst prepared by charging 12.39 g of sponge nickel and 14.36 g of a 10% cupric sulfate solution into a 500 ml-volume glass-made reactor equipped with a condenser tube and after stirring the solution for 30 minutes, removing the supernatant. Before the distillation, the main products of the reaction solution were 2,3,5,6-tetrafluorobenzaldehyde and 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal. After the distillation, 110.7 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 85.6%).

  • 16
  • [ 5216-17-1 ]
  • [ 306739-71-9 ]
YieldReaction ConditionsOperation in experiment
With sulfuric acid; hydrogen; In methanol; EXAMPLE 1 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde Dimethylacetal To a 50 ml-volume glass-made reactor equipped with a condenser tube, 0.50 g of sponge nickel thoroughly replaced by methanol was added and then a mixed solution containing 3.53 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>, 4.08 g of 97% sulfuric acid and 19.78 g of methanol was added. After the vapor phase moiety was thoroughly purged with hydrogen gas, a balloon charged with hydrogen gas was fixed to the top of the condenser tube and the solution was stirred at 10 C. for 6 hours. The reaction solution was analyzed by gas chromatography and the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 65.9%. Subsequently, the solution was stirred at 25 C. overnight. Then, the conversion was 100%. From this reaction solution, the catalyst was filtered and after heating the filtrate at 60 C. for 2 hours, the methanol was distilled off. The residue was cooled to room temperature and 2.09 g of an oil layer comprising 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal was separated. The oil layer was analyzed by means of a gas chromatograph, as a result, 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal accounted for the area in percentage of 97.0% and the remaining was 2,3,5,6-tetrafluorobenzaldehyde. The 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal was identified by NMR and mass spectrometry. NMR (CDCl3, delta): 3.50 (6H, s), 5.65 (1H, s), 7.19 (1H, m) MASS: M+224
  • 17
  • [ 5216-17-1 ]
  • [ 19842-76-3 ]
YieldReaction ConditionsOperation in experiment
100% With formic acid;aluminum nickel; In methanol; water; Example 17 (Reaction for Conversion from Cyano Group to Aldehyde Group) Using 83 g of methanol, 21 g of water, 45 g of formic acid, 1.5 g of Raney nickel, and 5.0 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>, a reaction was carried out by a method similar to Example 15. When the reaction was carried out at 60 C. for 4 hours, the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 100% and the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 84%.
100% With acetic acid;aluminum nickel; In methanol; water; Example 18 (Reaction for Conversion from Cyano Group to Aldehyde Group) Using 91 g of methanol, 12 g of water, 45 g of acetic acid, and 0.25 g of Raney nickel, a reaction was carried out by a method similar to Example 17. When the reaction was carried out at 60 C. for 2 hours, the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 100% and the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 70%.
99.9% With sulfuric acid; In methanol; EXAMPLE 4 Preparation of 2,3,5,6-Tetrafluorobenzaldehyde Into a 2 L-volume glass-made reactor equipped with a condenser tube, 127.08 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> and 468.48 g of methanol were charged. While stirring the mixture in a water bath, a mixed solution containing 228.48 g of methanol and 146.88 g of 97% sulfuric acid was added dropwise. Subsequently, 9.33 g of sponge nickel thoroughly replaced with methanol was added, the vapor phase moiety was thoroughly purged with hydrogen gas, and then the solution was stirred at 20 C. for 2 hours under atmospheric pressure in a hydrogen atmosphere. The resulting reaction solution was treated through the same operation as in Example 3. After the distillation, 101.59 g of 2,3,5,6-tetrafluorobenzaldehyde having a purity of 99.9% was obtained as the main fraction oil layer (yield based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>: 78.5%).
  • 18
  • [ 19842-76-3 ]
  • [ 5216-17-1 ]
YieldReaction ConditionsOperation in experiment
Furthermore, it was found that 4.50 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.5%).
Furthermore, it was found that 4.20 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.3%).
Furthermore, it was found that 4.80 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.7%).
Furthermore, it was found that 4.54 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.5%).
Furthermore, it was found that 4.50 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.5%).
Furthermore, it was found that 4.40 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.4%).
Furthermore, it was found that 4.50 g of 2,3,5,6-tetrafluorobenzaldehyde was dissolved in the aqueous layer (yield based on 2,3,5,6-tetrafluorobenzonitrile: 3.5%).

  • 19
  • [ 5216-17-1 ]
  • [ 19842-76-3 ]
  • [ 4084-38-2 ]
YieldReaction ConditionsOperation in experiment
100% With acetic acid;aluminum nickel; In 1,4-dioxane; water; Example 19 (Reaction for Conversion from Cyano Group to Aldehyde Group) Using 82 g of dioxane, 21 g of water, 45 g of acetic acid, and 0.5 g of Raney nickel, a reaction was carried out by a method similar to Example 18. The conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 100% and the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 47%. The yield of 2,3,5,6-tetrafluorobenzyl alcohol was 2%.
57% With acetic acid;aluminum nickel; In methanol; water; Example 22 (Reaction for Conversion from Cyano Group to Hydroxymethyl Group) 83 g of methanol, 45 g of acetic acid, 21 g of water, 0.5 g of Raney nickel, and 5.0 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> were added to a 500 cc stainless steel autoclave equipped with a Teflon inner tube in a nitrogen atmosphere. The gas phase was sufficiently replaced with hydrogen gas, then the autoclave was sealed and heated to 60 C. The reaction was carried out for 2 hours, Next, 1.0 g of Raney nickel catalyst was newly added, the gas sufficiently replaced with hydrogen gas, then the pressure raised to 0.5 MPa (gauge pressure). The reaction was carried out at 80 C. for 2 hours again, then the reaction solution was analyzed by gas chromatography, whereupon the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 100%, the yield of 2,3,5,6-tetrafluorobenzyl alcohol (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 57%, and the yield of 2,3,5,6-tetrafluorobenzaldehyde was 2%.
44% With sulfuric acid;aluminum nickel; In methanol; Example 16 (Reaction for Conversion from Cyano Group to Aldehyde Group) Using 158 g of methanol, 5.7 g of concentrated sulfuric acid, and 5.0 g of Raney nickel, a reaction was carried out by a method similar to Example 15. When the reaction was carried out at 25 C. for 4 hours, the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 80%, the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 44%, and the yield of 2,3,5,6-tetrafluorobenzyl alcohol was 1%.
33% With sulfuric acid; acetic acid;palladium/activated carbon; Example 15 (Reaction for Conversion from Cyano Group to Aldehyde Group) 150 g of acetic acid, 50 g of 3N aqueous sulfuric acid solution, 0.875 g of 2% palladium/activated carbon, and 8.75 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> were added to a 500 cc glass three-necked flask with a reflux condenser in a nitrogen atmosphere. The gas phase was sufficiently replaced with hydrogen gas, then a hydrogen balloon was attached to the top portion of the reflux condenser and the reaction was carried out at 80 C. for 8 hours. The reaction solution was analyzed by gas chromatography, whereupon the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 59%, the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 33%, and the yield of 2,3,5,6-tetrafluorobenzyl alcohol was 7%.

  • 20
  • [ 5216-17-1 ]
  • [ 598-54-9 ]
  • [ 19842-76-3 ]
  • [ 4084-38-2 ]
YieldReaction ConditionsOperation in experiment
80% With acetic acid;aluminum nickel; In methanol; water; Example 14 (Reaction for Conversion from Cyano Group to Aldehyde Group) 0.5 g of Raney nickel, 0.31 g of a copper acetate 10 hydrate, and 50 ml of water were added to a 500 cc glass three-necked flask with a reflux condenser in a nitrogen atmosphere. The resulting mixture was stirred at 25 C. for 2 hours, then 50 ml of water and methanol were successively added and decanting performed to wash the catalyst. Further, 80 g of methanol, 100 g of acetic acid, and 5 g of water as the solvent and 8.75 g of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> were newly added. The gas phase was sufficiently replaced with hydrogen gas, then a hydrogen balloon was attached to the top portion of the reflux condenser and the reaction carried out at 25 C. for 6 hours. The reaction solution was analyzed by gas chromatography, whereupon the conversion of <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong> was found to be 100%, the yield of 2,3,5,6-tetrafluorobenzaldehyde (based on <strong>[5216-17-1]2,3,5,6-tetrafluorobenzonitrile</strong>) was 80%, and the yield of 2,3,5,6-tetrafluorobenzyl alcohol was 2%.
  • 21
  • [ 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.
  • 22
  • [ 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.
  • 23
  • [ 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.
  • 25
  • [ 824391-83-5 ]
  • [ 5216-17-1 ]
  • PtH(C6HF3CN)(P(C6H11)3)2 [ No CAS ]
  • [ 144717-67-9 ]
  • 26
  • [ 55664-33-0 ]
  • [ 5216-17-1 ]
  • PtH(C6F4CN)(P(C6H11)3)2 [ No CAS ]
  • 27
  • [ 824391-83-5 ]
  • [ 5216-17-1 ]
  • [ 144717-67-9 ]
  • PtH(C6F4CN)(P(C6H11)3)2 [ No CAS ]
  • 28
  • [ 773-82-0 ]
  • [ 68-12-2 ]
  • 4,4'-[(dimethylamino)methylene]bis(2,3,5,6-tetrafluorobenzonitrile) hydrochloride [ No CAS ]
  • [ 5216-17-1 ]
  • 29
  • [ 31469-84-8 ]
  • [ 68-12-2 ]
  • [ 1173285-22-7 ]
  • [ 5216-17-1 ]
  • 30
  • [ 5216-17-1 ]
  • [ 98-80-6 ]
  • [ 1178578-07-8 ]
  • 31
  • [ 5216-17-1 ]
  • [ 824-94-2 ]
  • [ 1234340-55-6 ]
  • 32
  • [ 5216-17-1 ]
  • [ 71-43-2 ]
  • [ 1178578-07-8 ]
  • 33
  • [ 872092-11-0 ]
  • [ 5216-17-1 ]
  • [ 1289638-97-6 ]
  • 34
  • [ 61582-64-7 ]
  • [ 5216-17-1 ]
  • [ 890016-48-5 ]
  • 35
  • [ 5216-17-1 ]
  • [ 52742-32-2 ]
  • [ 1304685-29-7 ]
 

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