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Structure of 838-88-0 * Storage: {[proInfo.prStorage]}
* 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.
Stage #1: With hydrogenchloride In water for 0.5 h; Microwave irradiation Stage #2: at 40℃; Microwave irradiation
(1) o-toluidine, water, 37percent hydrochloric acid was added to the reactor,The reaction was stirred for 30min,Wherein o-toluidine and hydrochloric acid molar ratio of 1: 1.2,O toluidine and water weight ratio of 1: 4; (2) 37percent formaldehyde solution was diluted to 10percent; (3) The reaction solution in step (1) and the formaldehyde solution in step (2) are respectively transported to two inlets of the microreactor through a advection pump,The volume flow ratio of the reaction solution of step (1) and the step formaldehyde of step (2)Control o-toluidine and formaldehyde molar ratio of 3: 1; (4 ) The two raw materials in contact with the microreactor, mixing and reaction,Outflow from the reactor outlet,The reaction temperature was controlled at 40 ° C,Micro-reactor liquid hourly space velocity of 3000h-1; (5) cooling the reaction solution to room temperature,Aqueous sodium hydroxide solution was added dropwise,To pH about 9,A large number of white precipitate precipitation,filter,drying,Get MDT crude;(6) crude MDT by ethanol recrystallization,filter,dry,Get MDT,Molar yield86percentPurity 99percent.
52.5%
at 159.84℃; for 1 h;
In a typical run, zeolite (9.0 g), formaldehyde (0.3 mol), and o-tolylamine (0.6–3 mol) were added into a 500 mL autoclave madein Weihai Zhengwei Machinery Equipment Corporation Ltd, China.The sealed reactor was purged with nitrogen and then heated up tothe designed temperaturewith stirring. After the reactionwent throughthe scheduled times, the product mixture was sampled for HPLCanalysis.
Reference:
[1] Patent: CN106986777, 2017, A, . Location in patent: Paragraph 0043-0055; 0057; 0059; 0061; 0063; 0065
[2] Catalysis Communications, 2014, vol. 45, p. 69 - 73
[3] Journal of the American Chemical Society, 1935, vol. 57, p. 887,889
[4] Journal of the American Chemical Society, 1934, vol. 57, p. 1944
[5] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1982, vol. 21, # 8, p. 721 - 723
[6] Revue Roumaine de Chimie, 2005, vol. 50, # 9-10, p. 791 - 798
[7] Patent: EP1403241, 2004, A1, . Location in patent: Page 3; 4
[8] Patent: CN105294448, 2016, A, . Location in patent: Paragraph 0037
Reference:
[1] Organic and Biomolecular Chemistry, 2015, vol. 13, # 38, p. 9742 - 9745
4
[ 50-00-0 ]
[ 95-53-4 ]
[ 54560-77-9 ]
[ 838-88-0 ]
[ 72621-64-8 ]
Reference:
[1] Journal of Molecular Catalysis A: Chemical, 2015, vol. 398, p. 95 - 106
5
[ 88919-92-0 ]
[ 636-21-5 ]
[ 838-88-0 ]
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1988, p. 1631 - 1636
6
[ 636-21-5 ]
[ 62001-35-8 ]
[ 838-88-0 ]
Reference:
[1] Synthesis, 1990, p. 341 - 346
7
[ 5293-94-7 ]
[ 95-53-4 ]
[ 838-88-0 ]
[ 611-21-2 ]
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1980, p. 1420 - 1426
8
[ 71893-15-7 ]
[ 95-53-4 ]
[ 838-88-0 ]
[ 67-64-1 ]
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1980, p. 1420 - 1426
9
[ 95-53-4 ]
[ 838-88-0 ]
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1988, p. 1631 - 1636
[2] Chemische Berichte, 1894, vol. 27, p. 1814
With ruthenium on aluminium oxide; ammonium aluminium sulfate; hydrogen; In tetrahydrofuran; at 160℃; under 60006 Torr; for 4h;Acidic conditions; Large scale;
2000 kg of <strong>[838-88-0]3,3'-dimethyl-4,4'-diaminodiphenylmethane</strong> and 2000 kg of tetrahydrofuran were added to an autoclave having a volume of 6000 L, and then 100 kg of a 5% Ru/Al 2 O 3 catalyst and 100 kg of ammonium aluminum sulfate were added.After sealing, replace the air in the autoclave with hydrogen.Then, 6 MPa of hydrogen was introduced, and the autoclave was heated to 160 C. The hydrogen valve was adjusted to maintain the pressure in the autoclave at 8 MPa and the reaction was vigorously stirred for 4 hours.After cooling, sample and measure by gas chromatography-mass spectrometry.The detection result was that the conversion ratio of <strong>[838-88-0]3,3'-dimethyl-4,4'-diaminodiphenylmethane</strong> was 100%, and the MACM yield was 99.4%.
With hydrogen;ruthenium(IV) oxide hydrate; silica gel; at 230 - 240℃; under 150015 Torr; for 672h;
EXAMPLE 5Example 5 demonstrates a continuous hydrogenation by the process according to the invention.The preparation of the Ru(IV) oxide hydrate was carried out according to example 1 in DE 21 32 547, with the only exception that the final drying under reduced pressure was omitted. To prepare the catalyst suspension, 5500 g of the filtercake thus prepared (with 579 g of Ru, calculated 100%) and 280 g of hydrophobic SiO2 (Sipernat D17 from Evonik-Degussa GmbH) were added to a stirred vessel and mixed intensively with 150 kg of a liquid product mixture (output of the hydrogenation reactor), such that the suspension obtained comprised 0.37% by weight of Ru.The performance of the hydrogenation was performed in a continuous production plant with a cooled high-pressure bubble column reactor. 500 kg/h of a liquid melt of bis(4-aminophenyl)methane and 6.7 kg/h of the catalyst suspension were fed continuously into this reactor. The pressure in the reactor was regulated to 200 bar by replenishing pure hydrogen. The temperature in the reactor was kept constant within the range from 230 to 240 C. by cooling.The product mixture exiting from the reactor was decompressed and cooled to a temperature of 100 C. The analysis of the product mixture by means of gas chromatography gave the following values (concentration data in % by weight): The hydrogenation was conducted over a period of four weeks under constant conditions without any decline in the reactivity or else a blockage of the reactor as a result of solid sedimentation being observed. Without addition of the inorganic additives, sediments which disrupt production and lead to a decrease in the yield and selectivity generally occur after only one week.
With hydrogen;ruthenium(IV) oxide hydrate; at 240 - 248℃; under 150015 Torr;Industry scale;
EXAMPLE 2The reactor system used was that described in Example 1.The feedstock used for the hydrogenation was a melt of bis(4-amino-3-methylphenyl)methane (?o-toluidine base?) having a purity of approx. 99%. The reactant was used as a melt (melting point approx. 160 C.) without further dilution by a solvent.The catalyst used was ruthenium(IV) oxide hydrate, prepared according to Example 1 in DE 21 32 547. The catalyst was again suspended in liquid reactor effluent, so as to give rise to an Ru concentration of 0.37% by weight in this suspension.750 kg/h of a melt of o-toluidine base were fed continuously to the reactor at a temperature of 180 C., as were 10 kg/h of the catalyst suspension. The pressure in the reactor was regulated to 200 bar by replenishing pure hydrogen into the pumped circulation system. The temperature in the reactor was 240 C. at the bottom of the reactor, 245 C. below the lowermost perforated plate and 248 C. at the uppermost point in the reactor. The gas-liquid mixture leaving at the top was separated in a separator. The liquid obtained was drawn off under level control, decompressed and cooled to 80 C. The gas obtained in the separator was completely fed back to the mixing nozzle and to the lower part of the reactor in an amount of 5000 m3 (STP)/h.The analysis of the liquid product mixture by means of gas chromatography gave the following values (concentration data in % by weight): Analysis of reaction effluent % by weight Low-boiling by-products 3.5 High-boiling by-products 1.3 End product 95.1 Intermediate 0.08 Starting material 0.02 End product: bis(4-amino-3-methylcyclohexyl)methane Intermediate: (4-amino-3-methylcyclohexyl)(4-amino-3-methylphenyl)methane Starting material: bis(4-amino-3-methylphenyl)methaneThe conversion of the feedstock was >99.9% with a selectivity for the end product of approx. 95%.
Hydrogenation;
Example 2; Hydrogenation of Optionally Substituted MDA to Cycloaliphatic Amines
With hydrogen; In tetrahydrofuran; at 220℃; under 150015 Torr; for 8h;
A 300 mL pressure reactor is initially charged with 1.2 g of the catalyst A prepared according to Example 1.1 in a catalyst insert basket, which are admixed with 160 g of a 12% solution of ortho-toluidine base (2,2?-dimethyl-4,4?-methylenebis(aniline)) in THF. The hydrogenation is performed with pure hydrogen at a constant pressure of 200 bar and a temperature of 220 C. Hydrogenation is effected for 8 h. The reactor is subsequently decompressed. The conversion of o-toluidine base is 100% (GC column: DB-1, length 30 m, layer thickness 1 mum; temperature program: from 150 C. at 8 C./min to 280 C.). The selectivity for dimethyldicycan (2,2?-dimethyl-4,4?-methylenebis(cyclohexylamine)) is 89.1 area %.
(1) o-toluidine, water, 37% hydrochloric acid was added to the reactor,The reaction was stirred for 30min,Wherein o-toluidine and hydrochloric acid molar ratio of 1: 1.2,O toluidine and water weight ratio of 1: 4; (2) 37% formaldehyde solution was diluted to 10%; (3) The reaction solution in step (1) and the formaldehyde solution in step (2) are respectively transported to two inlets of the microreactor through a advection pump,The volume flow ratio of the reaction solution of step (1) and the step formaldehyde of step (2)Control o-toluidine and formaldehyde molar ratio of 3: 1; (4 ) The two raw materials in contact with the microreactor, mixing and reaction,Outflow from the reactor outlet,The reaction temperature was controlled at 40 C,Micro-reactor liquid hourly space velocity of 3000h-1; (5) cooling the reaction solution to room temperature,Aqueous sodium hydroxide solution was added dropwise,To pH about 9,A large number of white precipitate precipitation,filter,drying,Get MDT crude;(6) crude MDT by ethanol recrystallization,filter,dry,Get MDT,Molar yield86%Purity 99%.
52.5%
With zeolite H; at 159.84℃; for 1h;
In a typical run, zeolite (9.0 g), formaldehyde (0.3 mol), and o-tolylamine (0.6-3 mol) were added into a 500 mL autoclave madein Weihai Zhengwei Machinery Equipment Corporation Ltd, China.The sealed reactor was purged with nitrogen and then heated up tothe designed temperaturewith stirring. After the reactionwent throughthe scheduled times, the product mixture was sampled for HPLCanalysis.
In einem 2 l-Ruehrbehaelter mit Umpumpkreislauf und Rueckflusskuehler werden 400 g (3,72 mol) o-Toluidin (Reinheit > 99,5 %) vorgelegt und bei 60C mit 435,6 g 30 gew.-%-iger waessriger Salzsaeure (3,58 mol) versetzt, entsprechend einem Saeure/o-Toluidin-Verhaeltnis von 0,98. Bei dieser Temperatur wird ueber einen Zeitraum von 60 Minuten die in der Tabelle angegebene Menge einer 37 gew.-%-igen waessrigen Formaldehydloesung zudosiert. Nach Beendigung der Formaldehyd-Zugabe wird die Temperatur innerhalb von 30 Minuten linear auf 95C erhoeht und 240 Minuten bei 95C gehalten. Anschliessend wird zur Neutralisation ein Ueberschuss 25 gew.-%-ige NaOH der Reaktionsmischung zugegeben, wobei das Reaktionsprodukt als Feststoff ausfaellt. Das Produkt wird zur Entfernung von NaCl mehrmals mit Wasser gewaschen. Der salzfrei gewaschene Roh-Austrag wird anschliessend destillativ aufgearbeitet. Dabei wird zunaechst Wasser und anschliessend o-Toluidin abdestilliert. Die Reindestillation von 4,4`-Diaminoditolylmethan wird bei 260C Sumpftemperatur und 0,2 bis 0,3 mbar durchgefuehrt. Es wird eine Leichtsieder-Fraktion, im wesentlichen bestehend aus o-Toluidin, eine Mittelsieder-Fraktion, im wesentlichen bestehend aus 4,4'- und 2,4`-Diaminoditolylmethan, und ein oligomerer Destillationsrueckstand erhalten.
With Hbeta 100 zeolite; at 5 - 10℃; for 13h;Molecular sieve;
The Hbeta-100 zeolite (silica to alumina ratio 100) pressed powder, sieved to 10-16 mesh particles, each 20mL (8.1g) were placed in a fixed bed I, II in. I maintaining the temperature of the fixed bed 160 , fixed bed II holding temperature 180 ,Then press LHSV 6h-1, n (o-toluidine): n (formaldehyde) 8.00 (molar ratio) was pumped into the 99% of o-toluidine and 37% formaldehyde. After 1h the reaction was taken the feed 100g, stirred at 5-10 cooled 12h, filtered, the filter cake washed with a small amount of ethanol at 120 after drying, 21.3 g of a white solid, HPLC Assay for sampling, the mass percentage of each substance content of the: o-toluidine 0.5%, MDT90.8%, the intermediate 2-methyl-4- (o-tolylamino-methyl) phenylamin0.6%, other (including N, N'-Di-o-toyl-methanediamine , 2methyl-6- (o-tolylamino-methyl) phenylamine, containing three benzene polymers, etc.) 8.7%; MDT yield of 72.5%. After filtration, the mother liquor obtained after standing points to the water layer was 8.7g organic phase mother liquor 70.0g, with liquid detection, each substance mass content: o-toluidine 71.2%, MDT5.7%, intermediate 5.2% other 17.9%.
Specific examples of the amine compound include n-hexylamine, ... 4-methylaniline, 4-nitroaniline, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine,
deuterated 4,4'-methylene-di-o-toluidine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
45%
With water-d2;platinum on carbon; at 180℃; for 24h;Product distribution / selectivity;
Reference Example 10 Synthesis of Deuterated 4,4'-methylene di-o-toluidine 4,4'-methylene di-o-toluidine of 20 g (0.09 mol) and 5% Pt/C of 4 g were added to deuterated water (D2O) of 680 mL and subjected to reaction at about 180 C. for about 24 hours. After termination of the reaction, the reaction product was purified similarly as in Reference Example 1 to obtain deuterated 4,4'-methylene di-o-toluidine of 9 g (yield: 45%). The obtained deuterated 4,4'-methylene di-o-toluidine was subjected to structural analysis by measuring its 1H-NMR and 2H-NMR spectra to show an average deuteration ratio of 81%.
30%
With water-d2;platinum on carbon; palladium 10% on activated carbon; at 180℃; for 24h;Product distribution / selectivity;
Reference Example 2 Synthesis of Deuterated 4,4'-methylene di-o-toluidine 4,4'-Methylene di-o-toluidine of 20 g (0.09 mol) and a mixed catalyst of 6 g composed of 10% Pd/C of 2 g and 5% Pt/C of 4 g were added to deuterated water (D2O) of 680 mL and subjected to reaction at about 180 C. for about 24 hours. After termination of the reaction, the reaction solution was extracted with ethyl acetate, followed by filtering off the mixed catalyst. The obtained filtrate was dried using magnesium sulfate, concentrated under reduced pressure and then purified by column chromatography to obtain deuterated 4,4'-methylene di-o-toluidine of 6.0 g (yield: 30%). The obtained deuterated 4,4'-methylene di-o-toluidine was subjected to structural analysis by measuring its 1H-NMR and 2H-NMR spectra to show an average deuteration ratio of 81%.
Beispiel 1 bis 7; In einem 2 l-Ruehrbehaelter mit Umpumpkreislauf und Rueckflusskuehler werden 400 g (3,72 mol) o-Toluidin (Reinheit > 99,5 %) vorgelegt und bei 60C mit 435,6 g 30 gew.-%-iger waessriger Salzsaeure (3,58 mol) versetzt, entsprechend einem Saeure/o-Toluidin-Verhaeltnis von 0,98. Bei dieser Temperatur wird ueber einen Zeitraum von 60 Minuten die in der Tabelle angegebene Menge einer 37 gew.-%-igen waessrigen Formaldehydloesung zudosiert. Nach Beendigung der Formaldehyd-Zugabe wird die Temperatur innerhalb von 30 Minuten linear auf 95C erhoeht und 240 Minuten bei 95C gehalten. Anschliessend wird zur Neutralisation ein Ueberschuss 25 gew.-%-ige NaOH der Reaktionsmischung zugegeben, wobei das Reaktionsprodukt als Feststoff ausfaellt. Das Produkt wird zur Entfernung von NaCl mehrmals mit Wasser gewaschen. Der salzfrei gewaschene Roh-Austrag wird anschliessend destillativ aufgearbeitet. Dabei wird zunaechst Wasser und anschliessend o-Toluidin abdestilliert. Die Reindestillation von 4,4`-Diaminoditolylmethan wird bei 260C Sumpftemperatur und 0,2 bis 0,3 mbar durchgefuehrt. Es wird eine Leichtsieder-Fraktion, im wesentlichen bestehend aus o-Toluidin, eine Mittelsieder-Fraktion, im wesentlichen bestehend aus 4,4'- und 2,4`-Diaminoditolylmethan, und ein oligomerer Destillationsrueckstand erhalten. Vergleichsbeispiel V1; Beispiel 6 wurde wiederholt, wobei das Molverhaeltnis Saeure/o-Toluidin nur 0,4 betrug. Die Zusammensetzung der Produktmischung in Abhaengigkeit des gewaehlten o-Toluidin-Formaldehyd-Verhaeltnisses wird durch die nachstehende Tabelle wiedergegeben. Gemaess Vergleichsbeispiel V1 wird deutlich mehr des 2,4'-Isomeren und deutlich weniger des 4,4'-Isomeren gebildet.
With pyridine; triphenyl phosphite; In 1-methyl-pyrrolidin-2-one; at 100℃; for 24h;
In an argon atmosphere, the compound (4) (0.20 g, 0.55 mmol) prepared in Example 1, <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> (1.12 g, 4.95 mmol) and isophthalic acid (0.91 g, 5.50 mmol) were mixed in an eggplant-shaped flask and dissolved by addition of dry N-methylpyrrolidinone (10.0 ml), pyridine (2.90 ml) and triphenyl phosphite (0.88 ml). The resultant solution was stirred at 100C for 24 hours. The reaction solution obtained was cooled to room temperature and poured into excess methanol to precipitate the obtained polymer. The precipitated polymer was filtered off and dried under reduced pressure to give 1.77 g of a polyamide copolymer having a phosphorylcholine group represented by the above formula PA-6 as light brown powder. The copolymer structure was identified by the 1H-NMR spectrum given below: 1H-NMR, delta(400 MHz, DMSO-d6, ppm): 2.13 (s, -CH3), 3.12 (s, N-CH3), 3.88 (m, -CH2-), 4.09 (s, -CH2-), 4.27 (m, -CH2-), 4.47 (m, -CH2-), 4.66 (m, -CH2-), 6.90 (m, -Ph-), 7.01 (m, -Ph-), 7.10 (m, -Ph-), 7.25 (m, -Ph-), 7.68 (m, -Ph-), 8.08 (m, -Ph-), 8.48 (m, -Ph-), 8.52 (m, -Ph-), 9. 10 (s, -NH-), 9.97 (s, -NH-). The composition ratio of m/n in PA-6 was determined to be 98/2 from the evaluation of the peak area ratio in the 1H-NMR spectrum. Gel permeation chromatography (solvent: dimethylformamide, standard: polystyrene) for PA-6 provided number-average molecular weight of 1.52x104 and weight-average molecular weight of 6.48x104. PA-6 showed a glass transition temperature (softening point) of about 205C as determined by differential scanning calorimetry. Also, PA-6 was found to have similar solubility characteristics to those of PA-1.
With pyridine; triphenyl phosphite; In 1-methyl-pyrrolidin-2-one; at 80℃; for 24h;
In an argon atmosphere, the compound (11) (0.150 g, 0.384 mmol) prepared in Example 3, <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> (0.174 g, 0.768 mmol) and isophthalic acid (0.0637 g, 0.383 mmol) were mixed in an eggplant-shaped flask and dissolved by addition of dry N-methylpyrrolidinone (1.53 ml), pyridine (0.12 ml) and triphenyl phosphite (0.40 ml). The resultant solution was stirred at 80C for 24 hours. The reaction solution obtained was cooled to room temperature and poured into excess methanol to precipitate the obtained polymer. The precipitated polymer was filtered off and dried under reduced pressure to give 0.30 g of a polyamide copolymer having a phosphorylcholine group represented by the above formula PA-5 as light brown powder. The copolymer structure was identified by the 1H-NMR spectrum given below: 1H-NMR, delta(400 MHz, DMSO-d6, ppm) : 2.13 (s, -CH3), 3.12 (S, N-CH3), 3.88 (m, -CH2-), 4.09 (s, -CH2-), 4.27 (m, -CH2-), 4.47 (m, -CH2-), 4.66 (m, -CH2-), 6.90 (m, -Ph-), 7.01 (m, -Ph-), 7. 10 (m, -Ph-), 7.25 (m, -Ph-), 7.68 (m, -Ph-), 8.08 (m, -Ph-), 8.48 (m, -Ph-), 8.52 (m, -Ph-), 9.10 (s, -NH-), 9.97 (s, -NH-). The composition ratio of x/y in PA-5 was determined to be 78/22 from the evaluation of the peak area ratio in the 1H-NMR spectrum. Gel permeation chromatography (solvent: dimethylformamide, standard: polystyrene) for PA-5 provided number-average molecular weight of 1.04x104 and weight-average molecular weight of 3.91x104. PA-5 showed a glass transition temperature (softening point) of about 180C as determined by differential scanning calorimetry. Also, PA-5 was found to have similar solubility characteristics to those of PA-1.
In 1-methyl-pyrrolidin-2-one; at -80 - 20℃; for 6h;
In an argon atmosphere, the compound (4) (0.37 g, 0.94 mmol) prepared in Example 1, <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> (1.91 g, 8.45 mmol) and isophthalic acid chloride (1.91 g, 9.39 mmol) were mixed in an eggplant-shaped flask and cooled to about -80C in an aceton-dry ice bath. Subsequently, the mixture was combined with dry N-methylpyrrolidinone (33.8 ml), and the mixture was allowed to react for 6 hours while the temperature was slowly raised to ambient. After the reaction, the reaction solution was poured into.excess ethanol to precipitate the polymer. The precipitated polymer was filtered off and dried under reduced pressure to give 2.02 g of a polyamide copolymer having a phosphorylcholine group represented by the above formula PA-1 as light brown powder. The copolymer structure was identified by the 1H-NMR spectrum given below: 1H-NMR, delta(400 MHz, DMSO-d6, ppm): 2.21 (s, -CH3), 3.08 (S, N-CH3), 3.55 (m, -CH2-), 3.89 (s, -CH2-), 4.17 (m, -CH2-), 4.52 (m, -CH2-), 7.08 (m, -Ph-), 7.15 (m, -Ph-), 7.28 (m, -Ph-), 7.65 (m, -Ph-), 8.13 (m, -Ph-), 8.27 (m, -Ph-), 8.53 (m, -Ph-), 8.72 (m, -Ph-), 8.87 (m, -Ph-), 9.98 (s, -NH-). The composition ratio of x/y in PA-1 was determined to be 91/9 from the evaluation of the peak area ratio in the 1H-NMR spectrum. Gel permeation chromatography (solvent: dimethylformamide, standard: polystyrene) for PA-1 provided number-average molecular weight of 5.50x103 and weight-average molecular weight of 1.91x104. PA-1 showed a glass transition temperature (softening point) of about 215C as determined by differential scanning calorimetry, indicating sufficient heat resistance for medical device applications.
In 1-methyl-pyrrolidin-2-one; at -80 - 20℃; for 4h;Cooling with acetone-dry ice;
<Synthesis of polyamide> In an argon atmosphere, <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> (1.00 g, 4.42 mmol) and isophthalic acid chloride (0.901 g, 4.42 mmol) were mixed in an eggplant-shaped flask and cooled to about -80C in an aceton-dry ice bath. Subsequently, the mixture was combined with dry N-methylpyrrolidinone (8.9 ml), and the newly formed mixture was allowed to react for 4 hours while the temperature was slowly raised to ambient. After the reaction, the reaction solution was poured into excess ethanol to precipitate the obtained polymer. The precipitated polymer was filtered off and dried under reduced pressure to give 1.54 g of a polyamide represented by the above formula PA-0 as white powder. The structure was identified by the 1H-NMR spectrum given below: 1H-NMR, delta(400 MHz, DMSO-d6, ppm): 2.21 (6H, s, -CH3), 3.90 (2H, s, -CH2-), 7.08 (2H, d, J=1.95 Hz, -Ph-), 7.13 (2H, s, -Ph-), 7.28 (2H, d, J=1.95Hz, -Ph-), 7.63 (1H, t, J=7.08 Hz), 8.14 (2H, d, J=7.08 Hz), 8.55 (1H, s, -Ph-), 9.96 (2H, s, -NH-).
4,4'-di(benzylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane 4,4'-Diamino-3,3'-dimethyldiphenylmethane (0.566 g, 2.5 mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of benzylisothiocyanate (0.746 g, 5 mM) was added. The mixture was stirred at 80 C. for 10 minutes. After cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.00 g (77.7% yield) of a pale pink crystal of compound A-19. Melting point: 187 C. 1 H-NMR (DMSO-d6) ppm delta=2.12 (6H, s, phi-CH3 x 2) delta=3.83 (2H, s, phi-CH2 -phi) delta=4.68 (4H, d, J=5.0, phi-CH2 -- x 2) delta=7.06-7.34 (16H, m, --C6 H3 -- x 2, C6 H5 -- x 2) delta=7.84 (2H, broad s, --CH2 NH-- x 2) delta=9.12 (2H, broad s, --NH-- x 2)
4,4'-di(benzoylthiocarbamoylamino)-3,3'-dimethyldiphenylmethane 4,4'-Diamino-3,3'-dimethyldiphenylmethane (0.566 g, 2.5 mM) was dissolved in 10 ml of ethyl acetate, and 2 equivalents of benzoylisothiocyanate (0.816 g, 5 mM) was added. The mixture was stirred at 80 C. for 10 minutes. After cooling, the reaction mixture was filtered, and washed with ethyl acetate/n-hexane to obtain 1.24 g (89.7% yield) of a pale pink crystal of compound A-20. Melting point: 220 C. (dec.) 1 H-NMR (DMSO-d6) ppm delta=2.24 (6H, s, phi-CH3 x 2) delta=3.92 (2H, s, phi-CH2 --phi) delta=7.14-8.01 (16H, m, --C6 H3 -- x 2, C6 H5 -- x 2) delta=11.60 (2H, broad s, --NH-- x 2) delta=12.23 (2H, broad s, --NH-- x 2)
With hydrogen;silica gel; at 230℃; under 75007.5 - 202520 Torr; for 9h;Autoclave; Inert atmosphere;Product distribution / selectivity;
EXAMPLES 1 to 4; Examples 1 to 4 show the advantages of the present invention when using a chlorinated starting compound. Examples 1 to 4 were each carried out under the same reaction conditions.In example 1, no inorganic additive was added.In examples 2 to 4, in each case 5% by weight, based on the catalyst (calculated as elemental ruthenium) of inorganic additives was added. These were the following components:example 2: calcium stearate metal soap (particle size <200 mum)example 3: hydrophilic colloidal precipitated silica-spray-dried (spec. surface area approx. 190 m2/g, mean primary particle size approx. 18 nm, particle size to ISO 13320-1: 30 to 200 mum) (Sipernat 22 from Evonik-Degussa GmbH)example 4: hydrophobic, colloidal, chemically aftertreated silica (spec. surface area approx. 110 m2/g, mean primary particle size approx. 28 nm) (Sipernat D17 from Evonik-Degussa GmbH)Procedure: Experiments 1-4A roll autoclave with a glass insert was initially charged with 250 parts by weight of bis(4-amino-3-methylphenyl)methane, 2.5 parts by weight of catalyst suspension and if appropriate the particular amount of inorganic additive (examples 2 to 4). The catalyst suspension comprised 2% by weight, based on the suspension, of ruthenium catalyst (calculated as elemental ruthenium) and 0.134% by weight, based on the suspension, of bis(4-amino-3-methylphenyl)methane hydrochloride.The autoclave was first flushed with gaseous nitrogen, then hydrogen was injected in the cold state until a pressure of 100 bar was established. Then the rolling operation was begun and the temperature was simultaneously increased from room temperature to 230 C. within 4 hours. Additional hydrogen was then injected until a pressure of 270 bar was established.The roll autoclave was then operated at a temperature of 230 C. for 5 hours, in the course of which additional hydrogen was injected at hourly intervals in order to maintain the pressure of 270 bar.Thereafter, the pressure was adjusted once again to 270 bar of hydrogen and both the rolling drive and the heating were switched off.Once the reaction mixture had reached room temperature, the autoclave was decompressed, and the reaction mixture was removed and the catalyst and inorganic additive were filtered off.The filtrate was then subjected to a fractional distillation under reduced pressure.The results obtained in each case are reproduced below (concentration data in % by weight):
2-methyl-6-(o-tolylaminomethyl)phenylamine[ No CAS ]
[ 54560-77-9 ]
[ 838-88-0 ]
[ 72621-64-8 ]
Yield
Reaction Conditions
Operation in experiment
With hydrogenchloride; In water; at 159.84℃; for 1h;Autoclave; Inert atmosphere;Mechanism;
In a typical run, a certain amount of formaldehyde, o-tolylamin purified by distillation, and zeolite catalyst activated at 823 K for3 h were added into a 500 mL autoclave made in Weihai Zhengwei Machinery Equipment Corporation Ltd, China. The sealed reactor was purged with nitrogen and then heated up to the designed tem-perature with vigorous stirring. After the reaction went through the scheduled times, the product mixture was collected and sampled for HPLC analysis.
2,2'-bis-[4-(4-maleimidephenoxy)phenyl]propane[ No CAS ]
[ 838-88-0 ]
C50H44N4O6[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With 1-methoxy-2-propanol; In toluene; at 115 - 125℃; for 2h;
A thermometer, stirrer, the reaction vessel heating and cooling capacity capable of 5 l equipped with a reflux condenser with water measuring instrument, 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane: 1140.0g If, 4,4'-diamino-3,3'-dimethyl - diphenylmethane: 226.0G, and propylene glycol monomethyl ether: 540.5g and toluene: blending 328.9g, while stirring 115- 125 C It was refluxed for 2 hours. Take out a small amount of this reaction solution, GPC measurement (in terms of polystyrene, eluent: tetrahydrofuran) was carried out, elution time appeared in the vicinity of about 12.8 minutes 4,4'-diamino-3,3'-dimethyl - diphenylmethane peak derived from the disappeared, also the elution time peak different from the starting materials for synthesis appeared near about 11.3 minutes, compound of the following formula (XVII) was confirmed to have been manufactured.
With triethylamine; In dichloromethane;Inert atmosphere;
COMPARATIVE EXAMPLE 5 Synthesis of a compound C-05 (0151) (0152) 4,4?-methylenebis(2-methylaniline) (5 mmol) and triethylamine (3-10 equiv. to amine) were dissolved in dichloromethane (80 mL) under Ar. While the flask was immersed in a water bath, chlorodiphenylphosphine (20 mmol, 2 equiv. to amine) was slowly introduced, and the mixture was stirred overnight. After placing the mixture under vacuum to remove the solvent, THF was introduced, the mixture was sufficiently stirred, and a triethylammonium chloride salt was removed with an air-free glass filter. Remaining solvent was removed in the filtrate to obtain a product (compound D-05). (0153) 31P NMR (202 MHz, CDCl3): 61.7 (s) (0154) 1H NMR (500 MHz, CDCl3): 1.6 (6 H), 3.7 (2 H), 6.54 (2 H), 6.75 (2 H), 7.0-7.8 (42 H)
The following reaction, is carried out in a nitrogen atmosphere. In a flask equipped with a stirrer and cooling tubes, thiocyanic potassium titanate (wako purity chemical company) 2.5 parts, a part hydroxytetrahydrofuran 15, alkylbenzoylchloride (tokyo chemical company) 3.0 parts is dropped. After 30 minutes stirring at room temperature, 4,4 '-diamino -3,3' -(tokyo chemical company) diethyldiphenylmethane 2.17 part thrown at room temperature. Thereafter, by reacting 2 hours at room temperature, dropped into the crystallizer 30 part of ion-exchanged water. The resultant crystals is filtered, washed with ion-exchanged water in, the roughness of the compound represented by eq. (B-VIII-2) obtd. crystals. Further this coarse crystal suspension purified methanol, as represented by a wet cake eq. (B-VIII-2) 6.5 parts was obtained.
The following reaction was performed under a nitrogen atmosphere.2.5 parts of potassium thiocyanate (made by Wako Pure Chemical Industries, Ltd.)15 parts of tetrahydrofuran are fed into a flask with a cooling tube and stirring device.0.7 parts of benzamidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped.After stirring at room temperature for 30 minutes,At room temperature, 2.17 parts of <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed.After that, let it react at room temperature for 2 hours.30 parts of ion-exchanged water was dropped to crystallize.The resulting crystals were filtered and washed with ion-exchanged water.Thereby, a crude crystal of the compound represented by Formula (B-VIII-2) is obtained.The crude crystals were purified by suspension with methanol.On the other hand, 6.5 parts of the compound represented by formula (B-VIII-2) was obtained as a wet cake.
bis(4-amino-3-(1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl)-5-methylphenyl)methane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
41%
With toluene-4-sulfonic acid; In toluene; at 110℃; for 18h;Inert atmosphere; Autoclave;
In a 300 mL autoclave, 75 g (0.33 mol) of <strong>[838-88-0]4,4'-diamino-3,3'-dimethyldiphenylmethane</strong> as a starting compound, 200 g of toluene as a solvent, p-toluenesulfonic acid monohydrate 3 as a catalyst . lg, the atmosphere is replaced by nitrogen and sealed. The autoclave was heated to 110 C in an oil bath and 115 g of hexafluoroacetone (HFA) was added from the gas injection port of the autoclave in order to stir.After stirring for 18 hours, the autoclave was cooled to room temperature (20 C) and filtered. After washing with chloroform, dry under reduced pressure, bis(4-amino-3- (1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl) -5-methylphenyl) was obtained as a target compound of yield 41% ) 75.1 g (0.14 mol) of white powder of methane. The data measured by nuclear magnetic resonance spectroscopy (NMR) are shown below.