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[ CAS No. 626-17-5 ] {[proInfo.proName]}

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Chemical Structure| 626-17-5
Chemical Structure| 626-17-5
Structure of 626-17-5 * Storage: {[proInfo.prStorage]}
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Product Details of [ 626-17-5 ]

CAS No. :626-17-5 MDL No. :MFCD00001795
Formula : C8H4N2 Boiling Point : -
Linear Structure Formula :- InChI Key :LAQPNDIUHRHNCV-UHFFFAOYSA-N
M.W : 128.13 Pubchem ID :12276
Synonyms :

Calculated chemistry of [ 626-17-5 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 10
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.0
Num. rotatable bonds : 0
Num. H-bond acceptors : 2.0
Num. H-bond donors : 0.0
Molar Refractivity : 35.87
TPSA : 47.58 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -6.51 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.43
Log Po/w (XLOGP3) : 0.8
Log Po/w (WLOGP) : 1.43
Log Po/w (MLOGP) : 0.77
Log Po/w (SILICOS-IT) : 1.78
Consensus Log Po/w : 1.24

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.58
Solubility : 3.35 mg/ml ; 0.0262 mol/l
Class : Very soluble
Log S (Ali) : -1.38
Solubility : 5.33 mg/ml ; 0.0416 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -2.53
Solubility : 0.378 mg/ml ; 0.00295 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.35

Safety of [ 626-17-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P501-P260-P270-P264-P314-P301+P312+P330 UN#:N/A
Hazard Statements:H302-H373 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 626-17-5 ]

* 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.

  • Upstream synthesis route of [ 626-17-5 ]
  • Downstream synthetic route of [ 626-17-5 ]

[ 626-17-5 ] Synthesis Path-Upstream   1~18

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YieldReaction ConditionsOperation in experiment
69% at 270℃; for 4 h; Example 12
130 g (1200 mmol) of 2-methylglutaronitrile and 20 g (120 mmol) of isophthalic acid are introduced into a 250 ml glass reactor.
The white suspension is stirred and 0.32 g (2.4 mmol) of anhydrous aluminum chloride is added.
The mixture is gradually heated to 270° C. and is maintained under these conditions for 4 h.
During the rise in temperature, the isophthalic acid dissolves in the MGN.
The reaction medium is subsequently analyzed by GC. An RY percent for MGI of 76percent and a yield of 1,3-dicyanobenzene of 69percent are obtained.
Reference: [1] Patent: US2014/350265, 2014, A1, . Location in patent: Paragraph 0086-0088
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  • [ 141-43-5 ]
  • [ 34052-90-9 ]
YieldReaction ConditionsOperation in experiment
84% With sulfur; cobalt(II) nitrate In neat (no solvent) at 110℃; for 0.133333 h; Microwave irradiation General procedure: A mixture of nitrile (0.5 mmol), 2-aminoethanol (4) (0.65 mmol, 0.040 g), Co(NO3)2 (0.02 mmol, 0.036 g), and sulfur (0.05 mmol, 0.0016 g) was stirred at 90 C or subjected to microwave irradiation (90 C, 800 W) for appropriate time. For the synthesis of monooxazolines, dicyanobenzene (0.5 mmol), 2-aminoethanol (4) (0.65 mmol, 0.040 g), Co(NO3)2 (0.02 mmol, 0.036 g), and sulfur(0.05 mmol, 0.0016 g) was stirred at 90 C for 3 h or subjected to microwave irradiation (90 C, 800 W) for 3 min. For the synthesis of bis-oxazoline, dicyanobenzene (0.5 mmol), 2-aminoethanol (4) (2.6 mmol, 0.159 g), Co(NO3)2 (0.02 mmol, 0.036 g), and sulfur (0.05 mmol, 0.0016 g) was stirred at 110 C for 10 h or subjected to microwave irradiation (110 C, 800 W) for 8 min. After completionof the reaction (detected by TLC), the reaction mixture was cooled to room temperature, ethyl acetate (6 mL) was added and the catalyst was separated by the filtration. Following concentration under reduced pressure, the residue was purified by silica gel chromatography to give pure product (5a-r).
78% for 3 h; Heating / reflux Beispiel 1: Synthese von 2,2'-(1,3-Phenylen)bis-[4,5-dihydro-1,3-oxazol] In einem 1 L-Mehrhalskolben mit Fluegelruehrer, Sumpfkontaktthermometer, Wasserabscheider, Rueckflusskuehler, Feststoffdosierer (mit Foerderschnecke) und Stickstoffabdeckung wurden 244,3 g Ethanolamin (4 moleq), 318,5 g Xylol und 23,7 g Zink-2-ethylhexanoat bei Raumtemperatur vorgelegt. Die zunaechst 2-phasige Suspension wurde unter Ruehren bis auf Rueckflusstemperatur erhitzt. Anschliessend wurden 128,1 g (1 moleq) Isophtalodinitril (IPN) ueber einen Zeitraum von 2Std. kontinuierlich als Feststoff zum heissen Sumpf zudosiert. Dabei entstand Ammoniak als Abgas. Nach Ende der IPN-Dosierung wurde das nun einphasige Reaktionsgemisch ca. 1Std. bei Rueckflusstemperatur nachgeruehrt. Anschliessend wurde ueberschuessiges Ethanolamin (EA) mit Hilfe eines Wasserabscheiders durch azeotrope Destillation soweit wie moeglich aus dem Gemisch entfernt. Das sich als separate Phase im Wasserabscheider sammelnde EA konnte direkt in weiteren Ansaetzen eingesetzt werden. Nach Abkuehlen des Reaktionsgemisches auf 80 °C wurden 100 g i-PrOH zum Sumpf hinzugegeben. Anschliessend wurde das homogene Gemisch unter Ruehren weiter bis auf Raumtemperatur abgekuehlt. Die ausgefallenen Kristalle wurden ueber eine Glasfilternutsche abgesaugt, zweimal mit Cyclohexan gewaschen und anschliessend im Vakuum getrocknet. Aus den organischen Wasch- und Filtrationsloesungen konnten die verwendeten Loesungsmittel sehr einfach beispielsweise destillativ zurueckgewonnen und in weiteren Ansaetzen wieder eingesetzt werden. Man erhielt 2,2'-(1,3-Phenylen)bis-[4,5-dihydro-1,3-oxazol] in Form farbloser, rieselfaehiger Kristalle mit einer Reinheit >99,5 percent (laut GC). Zusammen mit dem aus dem Filtrat durch Nachfaellung isolierten Material lag die Gesamtausbeute an Zielprodukt bei 78 percent d. Th.. Der Weissgrad (Rz) betrug 75 percent (bezogen auf Bariumsulfat als Referenzstandard =100percent) und nach Waschen mit Isopropanol 82percent.
Reference: [1] Journal of Organic Chemistry, 2015, vol. 80, # 20, p. 9910 - 9914
[2] Synlett, 2005, # 18, p. 2747 - 2750
[3] Tetrahedron, 2013, vol. 69, # 32, p. 6591 - 6597
[4] Monatshefte fur Chemie, 2009, vol. 140, # 12, p. 1489 - 1494
[5] Journal of the Serbian Chemical Society, 2012, vol. 77, # 9, p. 1181 - 1189,9
[6] Patent: EP1548012, 2005, A2, . Location in patent: Page/Page column 5-6
[7] Tetrahedron Letters, 2002, vol. 43, # 28, p. 4955 - 4957
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  • [ 34052-90-9 ]
Reference: [1] Chemistry - An Asian Journal, 2013, vol. 8, # 7, p. 1408 - 1411
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  • [ 35963-33-8 ]
  • [ 83-41-0 ]
Reference: [1] Journal of the American Chemical Society, 1986, vol. 108, # 18, p. 5453 - 5459
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Reference: [1] Patent: US2005/215824, 2005, A1, . Location in patent: Page/Page column 3-4
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Reference: [1] Patent: US2012/116099, 2012, A1, . Location in patent: Page/Page column 8
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YieldReaction ConditionsOperation in experiment
92.8% With hydrogen In methanol; ammonia at 65℃; for 4 h; The same type of sponge nickel catalyst as used in Comparative Example 5 was charged into a glass tube with a 10-mm inner diameter in an amount of 3 g and dried at 200° C. in a nitrogen stream. Then, a mixed gas (methanol:nitrogen=4:96 by volume) was allowed to pass through the catalyst bed to pretreat the catalyst under the conditions of atmospheric pressure, 200° C., a flow rate of 1.5 NL/h, and 3 h. After the pretreatment, the catalyst was cooled to 30° C. in a nitrogen gas flow. The pretreated catalyst was slurried in 60 g of methanol in a nitrogen atmosphere. The hydrogenation of isophthalonitrile was conducted in the same manner as in Comparative Example 5 except for using the pretreated catalyst thus prepared. After 4 h of the hydrogenation, a part of the reaction liquid was sampled and analyzed. The conversion of isophthalonitrile was 100 mol percent, the yield of m-xylylenediamine was 92.8 mol percent, the yield of 3-cyanobenzylamine was 0.2 mol percent, and the yield of high-boiling condensation products was 7 mol percent.
87.3% With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃; EXAMPLE 1 Hydrogenation of Isophthalonitrile Into a 100-ml autoclave, were charged 3.2 g of isophthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of isophthalonitrile was 95.7 molpercent, the yield of 3-cyanobenzylamine was 87.3 molpercent and the yield of m-xylynenediamine was 7.7 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of Ni-diatomaceous earth pellets (manufactured by Nikki Chemical Co., Ltd.; Ni supported amount = 46percent by weight). The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of isophthalonitrile was 100 molpercent, the yield of 3-cyanobenzylamine was 0.2 molpercent and the yield of m-xylynenediamine was 89.4 molpercent EXAMPLE 4 Hydrogenation of Isophthalonitrile Into a 100-ml autoclave, were charged 3.2 g of isophthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of Pd-alumina pellets (manufactured by N.E. Chemcat Corporation; Pd content = 5percent by weight), and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of isophthalonitrile was 95.7 molpercent, the yield of 3-cyanobenzylamine was 87.3 molpercent and the yield of m-xylynenediamine was 7.7 molpercent. The reaction solution separated from the catalyst was charged into a 100-ml autoclave together with 10.0 g of liquid ammonia and 2.0 g of the catalyst A. The inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of isophthalonitrile was 100 molpercent, the yield of 3-cyanobenzylamine was 0.0 molpercent and the yield of m-xylynenediamine was 91.1 molpercent.
84.8% With hydrogen In methanol; ammonia at 65℃; for 4 h; autoclave Into a 300-ml SUS autoclave equipped with a stirrer, 10 g of isophthalonitrile was charged. Then, a slurry prepared by dispersing 3 g of a leached sponge nickel catalyst ("NDHT" available from Kawaken Fine Chemicals Co., Ltd.) in 60 g of methanol was charged and the autoclave was closed. After replacing the air in the autoclave with nitrogen, 30 g of ammonia was charged. The inner pressure was raised to 5 MPaG by hydrogen, and the hydrogenation was allowed to proceed at 65° C. The pressure was maintained at 5 MPaG by introducing hydrogen to supplement the consumed hydrogen. After 4 h of the hydrogenation, a part of the reaction liquid was sampled and analyzed. The conversion of isophthalonitrile was 100 mol percent, the yield of m-xylylenediamine was 84.8 mol percent, the yield of 3-cyanobenzylamine was 0.2 mol percent, and the yield of high-boilig condensation products was 15 mol percent.
Reference: [1] Patent: US2008/39658, 2008, A1, . Location in patent: Page/Page column 6
[2] Patent: EP1449825, 2004, A1, . Location in patent: Page 5
[3] Patent: US2008/39658, 2008, A1, . Location in patent: Page/Page column 6
[4] Patent: EP1454895, 2004, A1, . Location in patent: Page 8
[5] Patent: EP1454895, 2004, A1, . Location in patent: Page 5-7
[6] Patent: US2008/9654, 2008, A1, . Location in patent: Page/Page column 3-7
[7] Patent: US2008/9654, 2008, A1, . Location in patent: Page/Page column 7
[8] Patent: EP2325162, 2011, A1, . Location in patent: Page/Page column 8; 11
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YieldReaction ConditionsOperation in experiment
91% at 55℃; tube reactor; feed rate = 1.5 t/h; supplying hydrogen rate = 100 Nm3/h EXAMPLE 2 [0055] Hydrogenation Test [0056] A tubular insulated reactor having an inner diameter of 0.4 m was filled with 0.9 t of a commercially available catalyst (Ni-3266E manufactured by Harshaw Co., Ltd.; nickel content: about 50percent) to a packing height of 8 m. After activating the catalyst by reduction at 200° C. under a hydrogen flow, hydrogen gas and a hydrogenation raw material (IPN:MX:NH3=6:21:73 by weight) each pre-heated to 55° C. were fed into the reactor from the top thereof at respective feed rates of 100 Nm3/h and 1.5 t/h to allow the hydrogenation to proceed. The reaction pressure was 15 MPa. The reaction solution sampled from the outlet of the reactor was analyzed by gas chromatography. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 92 mol percent, and the yield of 3-cyanobenzyldiamine was 0.1 mol percent. The reaction was further continued by raising the pre-heating temperature only of the raw material so as to maintain the yield of 3-cyanobenzyldiamine at 0.5 mol percent or lower. After 28 days, the pressure difference between the inlet and the outlet of the catalyst layer was increased to 0.4 MPa, and the reaction was interrupted by stopping the supply of the hydrogenation raw material and hydrogen gas. [0057] Regeneration of Catalyst [0058] After cooling the catalyst layer to 45° C. and returning the inner pressure of the reactor to atmospheric pressure, nitrogen was flowed through the catalyst layer at a rate of 10 Nm3/h. The temperature of nitrogen gas being fed was raised from room temperature to 140° C. over 3 h. While maintaining the feed of nitrogen gas, hydrogen gas was fed at a rate of 0.1 Nm3/h. The temperature of the feed gas was raised to 200° C. over 2 h at a speed of 0.5° C./min. The average treating temperature during the temperature rise was 170° C. The temperature of the feed gas was successively raised to a final temperature of 340° C. over 6 h. While maintaining the feed gas at 340° C., the flow rate of hydrogen gas was increased stepwise to 3 Nm3/h and the feed amount of nitrogen gas was reduced stepwise to zero. During the course of maintaining the catalyst between 200° C. and 340° C., hydrogen gas was fed for 15 h. The feeding of hydrogen gas was carried out by monitoring the catalyst temperature. No steep temperature rise over 10° C./min was observed throughout the regeneration treatment. [0059] Hydrogenation Test after Regeneration [0060] After regenerating the catalyst, the hydrogenation was performed again by feeding the raw material of 55° C. under the same conditions as described above. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 91 mol percent, and the yield of 3-cyanobenzylamine was 0.1 mol percent, indicating that the regenerated catalyst was equivalent to the fresh catalyst in their catalytic activity. The pressure drop through the catalyst layer was 0.00 MPa, indicating that the pressure drop was completely got rid of. COMPARATIVE EXAMPLE 2 [0061] Hydrogenation Test [0062] A tubular insulated reactor having an inner diameter of 0.4 m was filled with 0.9 t of a commercially available catalyst (Ni-3266E manufactured by Harshaw Co., Ltd.; nickel content: about 50percent) to a packing height of 8 m. After activating the catalyst by reduction at 200° C. under a hydrogen flow, hydrogen gas and a hydrogenation raw material (IPN:MX:NH3=6:21:73 by weight) each pre-heated to 55° C. were fed into the reactor from the top thereof at respective feed rates of 100 Nm3/h and 1.5 t/h to allow the hydrogenation to proceed. The reaction pressure was 15 MPa. The reaction solution sampled from the outlet of the reactor was analyzed by gas chromatography. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 92 mol percent, and the yield of 3-cyanobenzyldiamine was 0.1 mol percent. The reaction was further continued by raising the pre-heating temperature only of the raw material so as to maintain the yield of 3-cyanobenzyldiamine at 0.5 mol percent or lower. After 31 days, the pressure difference between the inlet and the outlet of the catalyst layer was increased to 0.4 MPa, and the reaction was interrupted by stopping the supply of the hydrogenation raw material and hydrogen gas. [0063] Regeneration of Catalyst [0064] After reducing the inner pressure of the reactor to atmospheric pressure, hydrogen gas per-heated to 280° C. was fed to the catalyst layer at a rate of 10 Nm3/h. Immediately after beginning the feeding of hydrogen gas, a steep temperature rise occurred in the upper portion of the catalyst. The catalyst temperature was raised to 370° C. at highest to make the operation out of control. The temperature rise speed of the catalyst during the feed of hydrogen gas was 59° C. at highest. The feed of hydrogen gas was stopped and the catalyst layer was cooled to 140° C. by allowing nitrogen gas of room temperature to pass through the catalyst layer. [0065] Then, nitrogen gas and hydrogen gas were fed again at respective rates of 10 Nm3/h and 0.1 Nm3/h. The temperature of the feed gas was raised to 340° C. at a speed of 0.5° C./min, and finally the feed of the hydrogen-containing gas was continued at 340° C. for 2 h. While maintaining the feed gas at 340° C., the flow rate of hydrogen gas was increased stepwise to 3 Nm3/h and the feed amount of nitrogen gas was reduced stepwise to zero. Thereafter, the feed of gas was continued for 5 h in total. The feeding of hydrogen gas was carried out by monitoring the catalyst temperature. No steep temperature rise over 10° C./min was observed throughout the repetitive treatment. [0066] Hydrogenation Test after Regeneration [0067] After regenerating the catalyst, the hydrogenation was performed again by feeding the raw material of 55° C. under the same conditions as described above. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 82 mol percent, and the yield of 3-cyanobenzylamine was 6 mol percent, indicating the deterioration of the catalyst performance.
90.9% at 55℃; tube reactor; feed rate = 32 g/h; supplying hydrogen rate = 20 NL/h EXAMPLE 1 [0041] Preparation of Catalyst [0042] Into an aqueous solution prepared by dissolving 305.0 g of nickel nitrate hexahydrate (Ni(NO3)2.6H2O), 6.5 g of copper nitrate trihydrate (Cu(NO3)2.3H2O) and 7.1 g of chromium nitrate nonahydrate (Cr(NO3)3.9H2O) into 1 kg of pure water at 40° C., 29.6 g of diatomaceous earth was dispersed under stirring at 40° C. Then, an aqueous solution prepared by dissolving 128.6 g of sodium carbonate (Na2CO3) in 1 kg of pure water at 40° C. was poured into the resultant suspension under thorough stirring to prepare a precipitate slurry. After heated to 80° C. and held at that temperature for 30 min, the precipitate slurry was filtered to separate the precipitates, which were then washed with water, dried at 110° C. overnight, and then calcined in air at 380° C. for 18 h. The calcined powder was mixed with 3percent by weight of graphite and made into 3.0 mm 0.x.2.5 mm tablets by a tablet machine. The tablets were reduced at 400° C. under a hydrogen flow, and then, stabilized by an oxidation treatment overnight at a temperature from room temperature to 40° C. under a flow of diluted oxygen gas (oxygen/nitrogen={fraction (1/99)} by volume). Then, the tablets were crushed and sieved to have a particle size of 12 to 28 mesh, thereby obtaining a catalyst A. [0043] Hydrogenation Test [0044] A tube reactor having an inner diameter of 10 mm was filled with 10 g of the catalyst A (packing height: 130 mm). The catalyst A was activated by reduction at 200° C. under hydrogen flow. Then, a hydrogenation raw material consisting of a mixed solution of isophthalonitrile (IPN), m-xylene (MX) and ammonia (NH3) in a weight ratio of IPN:MX:NH3=6:54:40 was introduced into the tube reactor from the top thereof at a feed rate of 32 g/h. The hydrogenation was allowed to proceed at 55° C. under a reaction pressure of 7 MPa by supplying hydrogen gas under pressure in a rate of 20 NL/h. The reaction solution sampled from the outlet of the reactor was analyzed by gas chromatography. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 91.6 mol percent, and the yield of 3-cyanobenzyldiamine was 0.1 mol percent. The reaction was further continued by raising the temperature so as to maintain the above yields. After 24 days, the pressure difference between the inlet and the outlet of the catalyst layer was increased to 0.5 MPa, and the reaction was interrupted by stopping the supply of the hydrogenation raw material and hydrogen gas. [0045] Regeneration of Catalyst [0046] After cooling the catalyst layer to room temperature and returning the inner pressure of the reactor to atmospheric pressure, hydrogen was flowed through the catalyst layer at a rate of 5 NL/h. After heating the catalyst layer to 150° C., hydrogen was further allowed to continuously flow though the catalyst layer for 2 h (two-hour treatment at an average temperature of 150° C.). Thereafter, the temperature of the catalyst layer was raised to 260° C. at a rate of 4° C./min, and then, hydrogen was continuously flowed though the catalyst layer for 40 h. Finally, the catalyst layer was cooled to room temperature. [0047] Hydrogenation Test after Regeneration [0048] After regenerating the catalyst, the hydrogenation was performed again at 55° C. under the same conditions as described above. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 90.9 mol percent, and the yield of 3-cyanobenzylamine was 0.1 mol percent, indicating that the regenerated catalyst was equivalent to the fresh catalyst in their catalytic activity. The pressure drop through the catalyst layer was 0.00 MPa, indicating that the pressure drop was completely got rid of. COMPARATIVE EXAMPLE 1 [0049] Hydrogenation Test [0050] A tube reactor having an inner diameter of 10 mm was filled with 10 g of the catalyst A (packing height: 130 mm). The catalyst A was activated by reduction at 200° C. under hydrogen flow. Then, a hydrogenation raw material consisting of a mixed solution of isophthalonitrile (IPN), m-xylene (MX) and ammonia (NH3) in a weight ratio of IPN:MX:NH3=6:54:40 was introduced into the tube reactor from the top thereof at a feed rate of 32 g/h. The hydrogenation was allowed to proceed at 55° C. under a reaction pressure of 7 MPa by supplying hydrogen gas under pressure in a rate of 20 NL/h. The reaction solution sampled from the outlet of the reactor was analyzed by gas chromatography. The conversion of isophthalonitrile was 100percent, the yield of m-xylylenediamine was 90.9 mol percent, and the yield of 3-cyanobenzyldiamine was 0.1 mol percent. The reaction was further continued by raising the temperature so as to maintain the above yields. After 22 days, the pressure difference between the inlet and the outlet of the catalyst layer was increased to 0.5 MPa, and the reaction was interrupted by stopping the supply of the hydrogenation raw material and hydrogen gas. [0051] Regeneration of Catalyst [0052] After cooling the catalyst layer to room temperature and returning the inner pressure of the reactor to atmospheric pressure, hydrogen was flowed through the catalyst layer at a rate of 5 NL/h. After heating the catalyst layer to 150° C., hydrogen was further allowed to continuously flow though the catalyst layer for 2 h. Thereafter, the catalyst layer was cooled to room temperature. [0053] Hydrogenation Test after Regeneration [0054] After regenerating the catalyst, the hydrogenation was performed again at 55° C. under the same conditions as described above. The conversion of isophthalonitrile was 45.1percent, the yield of m-xylylenediamine was 0.1 mol percent, and the yield of 3-cyanobenzylamine was 28.6 mol percent. The pressure drop through the catalyst layer was 0.4 MPa.
Reference: [1] Patent: US2004/39232, 2004, A1, . Location in patent: Page 4-5
[2] Patent: US2004/39232, 2004, A1, . Location in patent: Page 4
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  • [ 100-81-2 ]
Reference: [1] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 7-8
[2] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 10
[3] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 9
[4] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 8-9
[5] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 7-9
[6] Patent: EP1762561, 2007, A1, . Location in patent: Page/Page column 9
[7] Patent: EP1857434, 2007, A2, . Location in patent: Page/Page column 8
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Reference: [1] Advanced Synthesis and Catalysis, 2010, vol. 352, # 14-15, p. 2394 - 2398
[2] Journal of Organic Chemistry, 2012, vol. 77, # 8, p. 4029 - 4034
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  • [ 539-48-0 ]
Reference: [1] Patent: EP1760070, 2007, A1, . Location in patent: Page/Page column 8
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  • [ 28442-78-6 ]
Reference: [1] Angewandte Chemie - International Edition, 2006, vol. 45, # 35, p. 5803 - 5807
[2] Journal of Organic Chemistry, 1982, vol. 47, # 13, p. 2681 - 2682
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Reference: [1] Journal of the American Chemical Society, 1994, vol. 116, # 10, p. 4240 - 4250
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  • [ 1184-88-9 ]
  • [ 154532-34-0 ]
Reference: [1] Tetrahedron, 2009, vol. 65, # 1, p. 263 - 269
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  • [ 85-01-8 ]
  • [ 1184-88-9 ]
  • [ 56666-55-8 ]
  • [ 154532-34-0 ]
Reference: [1] Tetrahedron, 2009, vol. 65, # 1, p. 263 - 269
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  • [ 863868-34-2 ]
YieldReaction ConditionsOperation in experiment
5.6 g With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine In tert-butyl methyl ether at 80℃; for 1 h; Inert atmosphere; Microwave irradiation General procedure: Typical procedure for the preparation of intermediates via Ir-catalysed boronic ester formation and subsequent Suzuki coupling with 4,6-dichloropyrimidine as exemplified by the preparation of Intermediate 24, 5-(6-chloropyrimidin-4- yl)benzene-l,3-dicarbonitrile.
Under N2, a solution of (l,5-cyclooctadiene)(methoxy)iridium(I) dimer (505 mg, 0.76 mmol), 4,4'-di-tert-butyl-2,2'-dipyridyl (409 mg, 1.52 mmol) and bis(pinacolato)diboron (13.4 g, 52.7 mmol) in TBME (135 mL) was prepared. A portion of this solution (15 mL) was added to isophthalonitrile (Intermediate 25, 700 mg, 5.46 mmol) and the mixture heated for 1 h at 80 °C in a microwave reactor. The reaction was repeated 8 more times on this scale and the combined reaction mixtures were concentrated in vacuo. Purification by gradient flash chromatography, eluting with 0-10percent EtOAc in hexane yielded 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)isophthalonitrile (5.6 g, 22.0 mmol).TLC: Rf 0.3, Hexane / Ethyl acetate 4: 1 1H NMR: (400 MHz, DMSO-cfe) δ: 1.33 (s, 12H), 8.25-8.27 (m, 2H), 8.60-8.61 (m, 1H)4,6-Dichloropyrimidine (Intermediate 2, 3.28 g, 22.0 mol), 5-(4,4,5,5-tetramethyl- l,3,2-dioxaborolan-2-yl)isophthalonitrile (5.6 g, 22.0 mmol) and cesium carbonate (14.4 g, 44.2 mmol) were dissolved in 1,4-dioxane / water (9: 1, 60 mL) and the mixture was degassed by purging with N2for 10 min. [1, 1 '- Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (806 mg, 1.10 mmol) was added and the reaction mixture was stirred at 90 °C for 3 h. After cooling to rt the reaction mixture was partitioned between H20 (250 mL) and EtOAc (150 mL), the phases were separated and the aqueous phase was extracted with EtOAc (2 x 150 mL). The combined organic phases were dried (Na2S04) and concentrated in vacuo. Purification by gradient flash chromatography, eluting with 0-15percent EtOAc in hexane yielded the title compound (1.70 g, 7.06 mmol) as a white solid.Data in table 1.
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 2, p. 861 - 864
[2] Patent: WO2015/8073, 2015, A1, . Location in patent: Page/Page column 39; 40
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  • [ 626-17-5 ]
  • [ 25015-63-8 ]
  • [ 863868-34-2 ]
Reference: [1] Journal of the American Chemical Society, 2005, vol. 127, # 30, p. 10539 - 10544
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  • [ 626-17-5 ]
  • [ 453565-55-4 ]
Reference: [1] Journal of Fluorine Chemistry, 2007, vol. 128, # 1, p. 29 - 33
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