Tag: M.W=100-200

136-90-3,Some common heterocyclic compound, 136-90-3, name is 4-Methoxy-3-methylphenylamine, molecular formula is C8H11NO, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

c) 2-Hvdroxyimino-Lambda/-(4-methoxy-3-methylphenyl)acetamideChloral hydrate (11.5 g, 70 mmol) and anhydrous sodium sulfate (60 g, 422 mmol) were added to vigorously stirred water (300 ml_). A slurry prepared by mixing hydroxylamine5 hydrochloride (23.0 g, 331 mmol) and 4-methoxy-3-methylphenylamine (10.0 g, 73 mmol) with aqueous hydrochloric acid (2.4 M, 250 ml.) was added to the above mixture. The resulting mixture was refluxed for 20 min and then allowed to stand at room temperature for 16 h. A precipitate formed and was collected by filtration. The solid was washed with water and dried to yield 2-hydroxyimino-N-(4-methoxy-3-methylphenyl)acetamide (6.7 g,10 32 mmol, 44%)Data for 2-hydroxyimino-N-(4-methoxy-3-methylphenyl)acetamide: MS (ESI) m/z: 209 ([M+H]+).

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 4-Methoxy-3-methylphenylamine, its application will become more common.

Reference:
Patent; AKZO NOBEL N.V.; PHARMACOPEIA DRUG DISCOVERY, INC.; WO2006/95014; (2006); A1;,
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14869-41-1, name is 2-(2-Chloroethoxy)acetic acid, belongs to ethers-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. 14869-41-1

27 mg, 0.34 mmol) of Intermediate 27a was added to 4 mL THF and stirred.Add 2-(2-chloro-ethoxy)acetic acid (48 mg, 0.34 mmol) and EEDQ (100 mg, 0.41 mmol), react at 60 ¡ã C for 4 hours, spin dry and add 5 mL of THF.NaH (40 mg, 1 mmol) was added portionwise with stirring, and reacted at room temperature for 5 hours.Add 0.2mL ammonium chloride solution, spin dry,The crude product was recrystallized from n-hexane andEtOAc to afford Intermediate 28z(174 mg, yield 76.0percent).

Statistics shows that 14869-41-1 is playing an increasingly important role. we look forward to future research findings about 2-(2-Chloroethoxy)acetic acid.

Reference:
Patent; Tianjin Pharmaceutical Institute Co., Ltd.; Wei Qunchao; Zheng Zhichao; Wang Songhui; Zheng Xuemin; Li Lingjun; Liu Lei; Yuan Jing; Zhang Shijun; Li Yuquan; Huang Changjiang; (38 pag.)CN109721539; (2019); A;,
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136-90-3,Some common heterocyclic compound, 136-90-3, name is 4-Methoxy-3-methylphenylamine, molecular formula is C8H11NO, traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

EXAMPLE 134 2-[N-(4-Methoxy-3-methylphenyl)-carbamyloxymethyl]-norborn-5-en-2-yl methyl ketone 2.1 g of 80% strength NaH suspension are added to a solution of 10.54 g (0.77 mole) of 4-methoxy-3-methylaniline in 30 ml of THF and the mixture is heated to 40 C. to complete the elimination of hydrogen. When this has ceased, a solution of 20.0 g (0.77 mole) of (2-acetylnorborn-5-en-2-yl)-methyl phenyl carbonate in 20 ml of tetrahydrofuran is added dropwise at room temperature, and the mixture is then stirred for 18 hours at 20 C. After having added a small amount of water, the solvent is stripped off and the residue is taken up in ether. The ether phase is washed repeatedly with 5% strength sodium hydroxide solution, and with water, and is dried over sodium sulfate. The crystalline crude product (11.8 g) is recrystallized from ethyl acetate; 6.4 g of 2-[N-(4-methoxy-3-methylphenyl)-carbamyloxymethyl]-norborn-5-en-2-yl methyl ketone, of melting point 121-122 C., are obtained. Analysis calc. 69.28% C, 7.04% H, 4.25% N, 19.4% O: found 69.4% C, 6.9% H, 4.3% N: C19 H23 NO4 M.Wt. =329.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 136-90-3, its application will become more common.

Reference:
Patent; BASF Aktiengesellschaft; US4335138; (1982); A;,
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22236-10-8, The chemical industry reduces the impact on the environment during synthesis 22236-10-8, name is 4-(Difluoromethoxy)aniline, I believe this compound will play a more active role in future production and life.

Example 26 1- [(6-Aminopyridin-3-yl)methyl]-3-{[4-(diffuromethoxy)phenyl]amino}-4-phenyl- 1H-PYRROLE-2, 5-dione A mixture of tert-butyl {5- [ (3-chloro-2, 5-dioxo-4-phenyl-2, 5-dihydro-lH-pyrrol-l- yl) methyl]pyridin-2-yl} carbamate (0.70 g, 1.7 mmol) and 4- (difluoromethoxy)-aniline (0.54 g, 3.4 mmol) in DMF (4 mL) was heated in a microwave reactor at 150C for eight min.. The sovent was evaporated and the residue was purified on a column (ISOLUTE SI, LOG/70 mL), using CH2Cl2 and then CH30H/CH2C12 (1: 99,2 : 98 and then 5: 95) as eluant, to give 0.4 g (54%) of the title COMPOUND. 1H NMR (400 MHz, CDC13) 8 7.99 (bs, 1H), 7.67-7. 62 (m, 2H), 7.14-7. 04 (m, 3H), 6.91 (d, J =8 Hz, 2H), 6.78 (d, J=8 Hz, 1H), 6.72 (d, J=9 Hz, 2H), 6.63 (d, J=9 Hz, 2H), 6.33 (t, J=74 Hz, 1H), 4.60 (s, 2H).

The chemical industry reduces the impact on the environment during synthesis 4-(Difluoromethoxy)aniline. I believe this compound will play a more active role in future production and life.

Reference:
Patent; ASTRAZENECA AB; WO2005/5417; (2005); A1;,
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Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 22236-10-8, name is 4-(Difluoromethoxy)aniline, This compound has unique chemical properties. The synthetic route is as follows., 22236-10-8

D. 7-(3-Chloropyridin-2-yl)-N-(4-(difluoromethoxy)phenyl)-5,6,7,8-tetrahydropyrido[3,4-d]pyrimidin-4-amine A mixture of 4-chloro-7-(3-chloropyridin-2-yl)-5,6,7,8-tetrahydropyrido[3,4-d]pyrimidine (0.103 g, 0.000366 mol) and 4-(difluoromethoxy)aniline (0.091 mL, 0.00073 mol) in acetonitrile (3 mL, 0.06 mol) was heated via microwave in a sealed tube at 160 C. for 10 minutes. After cooling to room temperature, the mixture was added to saturated sodium bicarbonate and extracted with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate. Concentrated to leave an oil. The residue was purified by flash chromatography over silica gel (ethyl acetate/hexane gradient 0 to 100%) to give 0.113 g of a light yellow solid. MS: M+H=404 1H NMR (DMSO-d6): delta 2.80 (t, J=5.6 Hz, 2H); 3.68 (t, J=5.6 Hz, 2H); 4.35 (s, 2H); 7.04 (dd, J=7.6 Hz, 4,7 Hz, 1H); 7.15 (d, J=9.0 Hz, 2H); 7.17 (t, J=75.0 Hz, 1H); 7.69-7.74 (m, 2H); 7.86 (dd, J=7.9 Hz, 1.6 Hz, 1H); 8.24 (dd, J=4.7 Hz, 1.6 Hz, 1H); 8.40 (s, 1H); 8.57 (s, 1H).

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Patent; Kelly, Michael G.; Janagani, Satyanarayana; Wu, Guoxian; Kincaid, John; Lonergan, David; Fang, YunFeng; Wei, Zhi-Liang; US2005/277643; (2005); A1;,
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929-75-9, name is 1,11-Diamino-3,6,9-trioxaundecane, belongs to ethers-buliding-blocks compound, is considered to be a conventional heterocyclic compound, which is widely used in drug synthesis. The chemical synthesis route is as follows. 929-75-9

Example 174 (3S)-3-(2-benzyl-3-chloro-7-oxo-2,4,5,7-tetrahydro-6H-pyrazolo[3,4-c]pyridin-6-yl)-N-(13-((3S)-3-(2-benzyl-3-chloro-7-oxo-2,4,5,7-tetrahydro-6H-pyrazolo[3,4-c]pyridin-6-yl)-5-methyl-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepin-8-yl)-13-oxo-3,6,9-trioxa-12-azatridec-1-yl)-5-methyl-4-oxo-2,3,4,5-tetrahydro-1,5-benzoxazepine-8-carboxamide To a mixture of (S)-2,4,6-trichlorophenyl 3-(2-benzyl-3-chloro-7-oxo-4,5-dihydro-2H-pyrazolo[3,4-c]pyridin-6(7H)-yl)-5-methyl-4-oxo-2,3,4,5-tetrahydrobenzo[b][1,4]oxazepine-8-carboxylate (50 mg) and tetrahydrofuran (2 mL) were added 2,2′-((oxybis(ethane-2,1-diyl))bis(oxy))diethanamine (7.28 mg), triethylamine (7.66 mg) and 4-dimethylaminopyridine (0.46 mg) at room temperature, and the mixture was stirred at 50C for 2 hr. The reaction mixture was diluted with ethyl acetate, washed with 0.1 M hydrochloric acid, saturated aqueous sodium hydrogencarbonate solution and saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/methanol) to give the title compound (27.1 mg). 1H NMR (300 MHz, CDCl3) delta2.66 (2H, dt, J = 15.9, 4.7 Hz), 3.03 (2H, ddd, J = 15.5, 10.4, 5.1 Hz), 3.29-3.39 (5H, m), 3.45-3.81 (17H, m), 4.15-4.27 (2H, m), 4.29-4.43 (2H, m), 4.52-4.71 (2H, m), 5.38 (4H, s), 5.85 (2H, dd, J = 11.5, 8.1 Hz), 7.11 (2H, brs), 7.18-7.35 (10H, m), 7.62-7.76 (4H, m).

Statistics shows that 929-75-9 is playing an increasingly important role. we look forward to future research findings about 1,11-Diamino-3,6,9-trioxaundecane.

Reference:
Patent; Takeda Pharmaceutical Company Limited; YOGO, Takatoshi; YOSHIKAWA, Masato; SAITOH, Morihisa; KATOH, Taisuke; SEKI, Tomohiro; NAKADA, Yoshihisa; (148 pag.)EP3366684; (2018); A1;,
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366-99-4, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 366-99-4, name is 3-Fluoro-4-methoxyaniline belongs to ethers-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Preparation 66A: 4-Bromo-3-fluoro-N-(3-fluoro-4- methoxyphenyl)benzenecarboximidamide To a solution of EtMgBr (48 mL, 42.55 mmol, 0.9 M) in THF (24 mL) was added a solution of 3-fluoro-4-methoxyaniline (3 g, 21.28 mmol) in THF (30 mL) at r.t. The mixture was stirred for 30 min at r.t. A solution of 4-bromo-3-fluorobenzonitrile (4.657 g, 23.40 mmol) in THF (20 mL) was added dropwise at r.t. and stirred overnight at r.t. LC/MS showed the reaction was completed, H20 was added and extracted with EA, dried, concentrated and purified by flash chromatography on silica gel (PE/EA=3/1 to EA) to afford 4-bromo-3-fluoro-N-(3-fluoro-4-methoxyphenyl)benzenecarboximidamide (4.68 g, 65percent). [M+H] Calc’d for Ci4HnBrF2N20, 341; Found, 341.

The synthetic route of 3-Fluoro-4-methoxyaniline has been constantly updated, and we look forward to future research findings.

Reference:
Patent; QUANTICEL PHARMACEUTICALS, INC.; CHEN, Young, K.; KANOUNI, Toufike; NIE, Zhe; STAFFORD, Jeffrey, Alan; VEAL, James, Marvin; (166 pag.)WO2016/4105; (2016); A1;,
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As we all know, there are many different methods for the synthesis of a compound, and people can choose the synthesis method that suits their own laboratory according to the actual situation. 4344-55-2 name is 4-Butoxyaniline, This compound is widely used in many fields, so it is necessary to find a new synthetic route. The downstream synthesis method of this compound is introduced below. 4344-55-2

1-bromonaphthalene: 22.78 g (110 mmol) 4-butoxyaniline: 8.26 g, 50 mmol Pd2 (dba)3: 1.007 g, 1.1 mmol P(t-Bu)3: 0.89 g (8.9 g in 10% hexane solution), 4.4 mmol tBuONa: 14.8 g, 154 mmol To a three-necked flask equipped with a reflux condenser, 1-bromonaphthalene, 4-butoxyaniline, Pd2 (dba)3, P(t-Bu)3, t-BuONa and toluene (150 ml) are added and stirred at 80 C. until the 4-butoxyaniline disappears as shown by HPLC analysis. After the reaction is completed, the reaction mixture is passed through a column packed with 6 inches of neutral alumina, and 2 L of toluene eluent is collected. The solvent is removed on rotary evaporator. The residue is extracted with 250 ml of diethyl ether, and the organic layer is washed with 3¡Á200 ml of brine. The organic layer is dried over MgSO4 and concentrated on a rotary evaporator. The crude product is recrystallized from isopropanol. The final product is an off-white powder with a purity of 98.5% as determined by HPLC; the yield is 54%.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 4-Butoxyaniline, and friends who are interested can also refer to it.

Reference:
Patent; SUMITOMO CHEMICAL COMPANY, LIMITED; US2012/264977; (2012); A1;,
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The chemical industry reduces the impact on the environment during synthesis 402-52-8, name is 1-Methoxy-4-(trifluoromethyl)benzene, I believe this compound will play a more active role in future production and life. 402-52-8

To chloro sulfuric acid (15 mL) was added l-methoxy-4-trifluoromethyl- benzene (3.0 g, 17 mmol) portionwise at 0C. The mixture was stirred at room temperature overnight. The mixture was poured into ice. the aqueous layer was extracted with EtOAc (50 mL x3). The extracts were dried over Na2S04 and the solution was filtered through a pad of silica gel, dried in vacuum to afford 500 mg (yield: 11%) of 2-methoxy-5-trifluoromethyl- benzenesulfonyl chloride as white solid. [00183] 1H NMR (DMSO-d6): delta = 7.90 (1H, d), 7.67 (1H, dd), 7.18 (1H, d), 3.84 (3H, s).

The chemical industry reduces the impact on the environment during synthesis 402-52-8. I believe this compound will play a more active role in future production and life.

Reference:
Patent; SANFORD-BURNHAM MEDICAL RESEARCH INSTITUTE; PINKERTON, Anthony, B.; DAHL, Russell; COSFORD, Nicholas, D.P.; MILLAN, Jose, Luis; WO2013/126608; (2013); A1;,
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1535-75-7, Each compound has different characteristics, and only by selecting the characteristics of the compound suitable for a specific situation can the compound be applied on a large scale. 1535-75-7, name is 2-(Trifluoromethoxy)aniline, This compound has unique chemical properties. The synthetic route is as follows.

General procedure: Pd(OAc)2 (20 mg, 0.09 mmol), (+/-)-BINAP (55 mg, 0.09 mmol), and DMF (5 mL) were charged in a round-bottom flask flushed with argon. The flask was evacuated and backfilled with argon. The mixture was stirred under argon for 30 min and added to a mixture of 27 (345 mg, 0.9 mmol), 2-trifluoromethoxyaniline (0.184 mL, 1.35 mmol), and K2CO3 (1.24 g, 8.97 mmol) in DMF (10 mL). The resulting mixture was stirred at 80 C for 4 h under argon. After cooling to room temperature, the reaction mixture was filtered on a pad of celite. The solvent was evaporated, the crude solid was purified by flash chromatography on silica gel (eluant: DCM/EtOH 90/10) to afford 210 mg (54%) of 31 as white solid.

If you are interested in these compounds, you can also browse my other articles.Thank you for taking the time to read this article. I hope you enjoyed it.

Reference:
Article; Caldarelli, Marina; Angiolini, Mauro; Disingrini, Teresa; Donati, Daniele; Guanci, Marco; Nuvoloni, Stefano; Posteri, Helena; Quartieri, Francesca; Silvagni, Marco; Colombo, Riccardo; Bioorganic and Medicinal Chemistry Letters; vol. 21; 15; (2011); p. 4507 – 4511;,
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