Month: March 2021

Reference of 956434-30-3, These common heterocyclic compound, 956434-30-3, name is tert-Butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate, its 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.

(step 1) To a solution of (2S)-butan-2-ol (0.32 mL) in toluene (8 mL) was added sodium hydride (0.28 g), and the resulting mixture was stirred at 70C for 15 min under a nitrogen atmosphere. A mixture of tert-butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (1.0 g), BINAP (0.066 g), Pd2(dba)3 (0.048 g) and toluene (8 mL) was added, and the resulting mixture was stirred at 100C for 2 hr under an argon atmosphere. The reaction solution was poured into water, and the resulting product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 0?40% ethyl acetate/hexane) to give tert-butyl 8-{[(1S)-1-methylpropyl]oxy}-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.73 g, 65%) as a white powder. 1H-NMR(CDCl3):delta0.94(3H,t,J=7.4Hz), 1.27(3H,d,J=6.3Hz), 1.42(9H,s), 1.63-1.75(2H,m), 3.76-3.86(2H,m), 4.21(2H,brs), 4.34-4.43(2H,m), 5.10(1H,brs), 6.39(1H,d,J=8.1Hz), 7.38-7.47(1H,m)

Statistics shows that tert-Butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate is playing an increasingly important role. we look forward to future research findings about 956434-30-3.

Reference:
Patent; Takeda Pharmaceutical Company Limited; EP2213675; (2010); A1;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Electric Literature of 85006-25-3, 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. 85006-25-3 name is tert-Butyl (tert-butoxycarbonyl)oxycarbamate, 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.

To an ice cooled (0 C) solution of tert-butyl N-(tert-butoxycarbonyloxy)carbamate (4.90 g, 21.01 mmol) in anhydrous DMF (30 mL) under nitrogen was added portion-wise 60% sodium hydride in mineral oil (540 mg, 22.5 mmol) and stirred for 30 min. The reaction mixture was treated with dropwise addition of a solution of [N-3-(3-fluoro -4-morpholinylphenyl)-2-oxo-5-oxazolidinyl] methyl methane sulfonate (5.90 g, 15.8 mmol) in DMF (70 mL). The reaction mixture was stirred to room temperature for 64 h. The reaction mixture was diluted with water (210 mL) and extracted with ethyl acetate (3 * 100 mL) and the EtOAc extract was diluted with hexane (60 mL) and washed with water, brine, dried (Na2SO4), filtered and concentrated to give the crude as a brown oil. Silica gel column chromatography eluted with EtOAc-Hexane 2:1 gave the titled compound 24 [17] as a pale yellow viscous oil (6.27 g, yield, 77.8%). 1H-NMR (DMSO-d6, 600 MHZ): delta 7.51 (dd, 1H, J = 15.0 Hz, 2.5 Hz, phenyl H), 7.19 (dd, 1H, J = 8.8 Hz, 2.5 Hz, phenyl H), 7.09 (t, 1H J = 9.6 Hz, phenyl H), 4.87 (m, 1H, oxazolidinone H), 4.15 (t, 1H, J = 4.6 Hz, oxazolidinone H), 3.97 (m, 1H, oxazolidinone H), 3.82 (m, 1H, methylene H), 3.72-3.76 (br t, 5H, morpholine H and methylene H), 2.97 (br t, 4H, morpholine H), 1.41-1.48 (br, 18H). MS 511.2 (M+).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, tert-Butyl (tert-butoxycarbonyl)oxycarbamate, and friends who are interested can also refer to it.

Reference:
Article; Phillips, Oludotun A.; D’Silva, Roselyn; Bahta, Teklu O.; Sharaf, Leyla H.; Udo, Edet E.; Benov, Ludmil; Eric Walters; European Journal of Medicinal Chemistry; vol. 106; (2015); p. 120 – 131;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Related Products of 1888-91-1,Some common heterocyclic compound, 1888-91-1, name is N-Acetylcaprolactam, molecular formula is C8H13NO2, 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.

The following five acetyl donating compounds were assessed at the outset: [0114] 1. N-acetoxysuccinimide [0115] 2. N-acetylsuccinimide [0116] 3. N-acetylcaprolactam [0117] 4. N,N,N,N-tetraacetylethyidiamine (TAED) [0118] 5. N,N,N-triacetylethylenediamine [0119] 6. Pentaacetylglucose [0120] Among these five compounds, only N-acetylcaprolactam is in the liquid state at ambient temperature. Some of the compounds are available on the market, although it was possible to carry out their synthesis by method available in the state of the art. [0121] From a preliminary assessment, it was observed that: [0122] Although poorly soluble in water, the first two compounds rapidly undergo perhydrolysis, once dispersed in a hydroalcoholic solution based on 3% w/w hydrogen peroxide; however, by being very reactive, they are highly sensitive to air moisture, so much so that their storage requires too severe conditions for use and above all for standard shipping. [0123] The third compound tends to separate at the bottom, once dispersed in a hydrophilic environment; however, it dissolves in the few moments after mixing owing to advancement of the perhydrolysis reaction and the solubilisation of the reaction by-products. This compound is also to be regarded as a medium fast rate N-acetylating agent and does not cause any particular problem, if suitably stored in tight-sealed vessels. [0124] The fourth compound is very well-known in the field of decontaminating, detergent and bleaching formulations and is a fast-rate acetylating agent even though it exhibits little solubility in water, particularly at ambient temperature and when the solution has a neutral-acidic pH. [0125] Finally, the fifth and the sixth compounds from a preliminary assessment were found to be weak acetylating agents and also poorly miscible with water.

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

Reference:
Patent; Preto, Andrea; Tabasso, Paolo; US2004/2616; (2004); A1;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Application of 98-64-6, These common heterocyclic compound, 98-64-6, name is 4-Chlorobenzenesulfonamide, its 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.

General procedure: The prepared TfOH-SiO2 (60 mg, containing 0.05 mmol TfOH) was added to the toluene (2 mL) solution of alkene (2 mmol or 4 mmol) and sulfonamide (1 mmol) and the reaction mixture was stirred at 70 oC (or 85 oC). The course of the reaction was monitored by TLC. After the completion of the reaction, the mixture was cooled to room temperature and the reactor was centrifuged (2000 r/min) for 2 min and the solution was removed by syringe. The catalyst was then washed with toluene (1 mL) twice with the same procedure and a new reaction was carried out by adding the new batch of alkene (2 mmol), sulfonamide (1 mmol) and toluene (2 mL) to the recovered catalyst. The solution containing the product was purified through a silica gel flash column to afford the product.

The synthetic route of 98-64-6 has been constantly updated, and we look forward to future research findings.

Reference:
Article; Liu, Pei Nian; Xia, Fei; Zhao, Zheng Le; Wang, Qing Wei; Ren, Yu Jie; Tetrahedron Letters; vol. 52; 46; (2011); p. 6113 – 6117;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Synthetic Route of 14062-80-7,Some common heterocyclic compound, 14062-80-7, name is 4-Chloro-N,N-dimethylbenzamide, molecular formula is C9H10ClNO, 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.

N’-cyanobenzimidamide (16.8 g, 115 mmol),Compound A-2 (21 g, 115 mmol) andPhosphorus oxychloride (12 mL, 128 mmol) was added to a solution ofAnd the mixture was added to 500 mL of acetonitrile, followed by stirring and refluxing for 1 hour. After cooling to room temperature, the resulting solid was filtered, washed with water and ethanol, and dried to give Compound A (27.6 g, yield 80%).

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

Reference:
Patent; LG Chem, Ltd.; Kang Min-yeong; Park Tae-yun; Cho Seong-mi; Moon Jeong-uk; Jeong Min-u; Lee Jeong-ha; Chae Mi-yeong; (30 pag.)KR2019/9211; (2019); A;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Application of 21440-97-1, The chemical industry reduces the impact on the environment during synthesis 21440-97-1, name is 6-Bromo-4,4-dimethyl-1,4-dihydrobenzo[d][1,3]oxazin-2-one, I believe this compound will play a more active role in future production and life.

With a thermometer,Add 40g compound 17, to the 1L three-neck bottle of the condenser28.7 g carbazole, 32.3 g K2CO3, 0.62 g 1,10-Phenanthroline,Then 450 ml of DMF was added.Replace the air in the reaction system with nitrogen,Add 0.45 g of CuBr under nitrogen protection.Heat to 120 C for 10 h,After the TLC was monitored, the starting material was completely reacted and the stirring was stopped and lowered to room temperature.The reaction system is added to 3 volumes of water,The product was precipitated by stirring and filtered.The filter cake was completely dissolved in 500 ml of dichloromethane (DCM) and washed 3 times with water.150ml each time. The organic phase is dried and concentrated.The crude product was passed through a silica gel column to give compound 18 as a white solid, 43.1 g, yield 80.6%.

In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, 6-Bromo-4,4-dimethyl-1,4-dihydrobenzo[d][1,3]oxazin-2-one, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Xi’an Ruilian New Materials Co., Ltd.; Sun Jun; Zhang Hongke; Liu Kaipeng; Yang Yan; Yang Dandan; Gao Renxiao; (34 pag.)CN108912138; (2018); A;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Related Products of 14437-03-7, A common heterocyclic compound, 14437-03-7, name is Methyl tosylcarbamate, molecular formula is C9H11NO4S, its 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.

General procedure: The 4-substituted methyl (phenylsulfonyl)carbamate was dissolved in the chosen alcohol (2 mL) in a microwave vial, which was closed using an aluminum open-top seal with PTFE-faced septum. The reaction mixture was heated under microwave irradiation at 100-120 oC for 20-60 min. The crude reaction mixture was concentrated under reduced pressure and the residue was purified using silica gel column chromatography to yield the desired (aryl)carbamate.

The basis of chemical reaction formula synthesis, the synthesis route is composed of some specific reactions and combined according to certain logical thinking. We look forward to the emergence of more reaction modes in the future.

Reference:
Article; Isaksson, Rebecka; Kumpi?a, Ilze; Larhed, Mats; Wannberg, Johan; Tetrahedron Letters; vol. 57; 13; (2016); p. 1476 – 1478;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Reference of 83922-54-7, A common heterocyclic compound, 83922-54-7, name is 4-(Methylsulfonamido)benzaldehyde, molecular formula is C8H9NO3S, its 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.

To a solution of the compound prepared in Reference Example 2 (100 mg) in dimethyl formamide (3 mL) was added acetic acid (16 muL) (or triethylamine (40 muL)). To the reaction mixture was added N-(4-formylphenyl)methanesulfonamide (56 mg) and sodium triacetoxyborohydride (82 mg). The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated, the obtained residue was purified by column chromatography on silica gel (ethyl acetate : methanol = 20 : 1-10 : 1) and 4N hydrogen chloride / ethyl acetate solution was added thereto. The reaction mixture was concentrated to give the compound of the present invention (72 mg) having the following physical data. TLC: Rf 0.67 (dichloromethane:methanol=5:1); NMR(CD3OD): delta 7.53, 7.34, 4.32, 4.15, 3.99, 3.74, 3.54-3.42, 3.33-3.16, 3.01, 2.49-2.24, 2.14- 1.91, 1.80-1.60, 1.40-1.15, 1.00-0.87.

The synthetic route of 83922-54-7 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; ONO PHARMACEUTICAL CO., LTD.; EP1541574; (2005); A1;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Electric Literature of 2360-20-5, A common heterocyclic compound, 2360-20-5, name is 3,4-Diaminobenzenesulfonamide, molecular formula is C6H9N3O2S, its 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 91 2-[4-(3-Chloro-4-fluoro-phenylsulfanyl)-phenyl]-1H-benzoimidazole-5-sulfonic Acid Amide. This compound was prepared according to the methods described in Example 22 and Scheme 3, substituting 4-(3-chloro-4-fluoro-phenylsulfanyl)-benzaldehyde for 4-(4-fluoro-phenoxy)-benzaldehyde, and 3,4-diamino-benzenesulfonamide for 3,4-diaminobenzamide. HPLC: Rt=8.57. MS (ESI+): mass calculated for C19H13ClFN3O2S2, 433.01; m/z found, 434.0 [M+H]+, 436.0 [M+H]+. 1H NMR (500 MHz, CD3OD): 8.23 (d, J=1.6, 1H), 8.05 (d, J=8.7, 2H), 7.96-7.94 (dd, J=8.6, 1.6, 1H), 7.81 (d, J=8.5, 1H), 7.67-7.65 (dd, J=6.9, 2.3, 1H), 7.52-7.46 (m, 1H), 7.45 (d, J=8.7, 2H), 7.35 (t, J=8.8, 1H).

The synthetic route of 2360-20-5 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; Arienti, Kristen L.; Axe, Frank U.; Breitenbucher, J. Guy; Huang, Liming; Lee, Alice; McClure, Kelly J.; US2003/176438; (2003); A1;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics

Application of 112101-81-2, A common heterocyclic compound, 112101-81-2, name is R-5-(2-Aminopropyl)-2-methoxybenzenesulfonamide, molecular formula is C10H16N2O3S, its 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 4:Preparation of By-Product (5-((R)-2-{Bis-[2-(2-ethoxy phenoxy)ethyI]amino}-propyl)-2-methoxy benzene sulfonamide)This example demonstrates how by-product 5-((R)-2-{Bis-[2-(2-ethoxyphenoxy) ethyl]amino}-propyl)-2-methoxybenzenesulfonamide is prepared by reacting the (R)- enantiomer of reactant-V according to prior processes. A round-bottomed flask is charged with 4.0 g (16.37 mmol) of (R)-reactant-V, 3.47 g (32.74 mmol) OfNa2CO4, 8.01 g (32.65 mmol) of the bromide form of reactant-VI, and 24 mL of N,N-dimethylformamide. Notably, alkyl phosphite solvent was not used in this example. The mixture is heated up to 80 C, and is stirred overnight at 80 C, and then the mixture is cooled down to about 20-25 C. EPO At this point, 40 mL of water and 40 mL of AcOEt are charged into the flask and the resulting mixture is then stirred for 30 minutes and left to decant. The organic phase is separated and then charged again into the flask, is reintroduced in the flask and washed with slightly acidic water (pH 5). The mixture is let to decant and the organic phase is dried with Na2SO4 and the solvent evaporated to obtain 8.96 g of crude 5-((R)-2-{Bis-[2-(2- ethoxyphenoxy)ethyl]amino}-propyl)-2-methoxybenzene sulfonamide. The crude product was purified by silica gel column chromatography (AcOEt as eluent) to obtain 6.29 g of 5- ((R)-2- {Bis-2-(2-ethoxyphenoxy)ethyl]amino } -propyl)-2-methoxybenzenesulfonamide, which still was unpurified and contained unused reactant-VI. A second silica gel column chromatography (CHCI3 as eluent) was performed to obtain 6.00 g of purified 5-((R)-2-{Bis- [2-(2-ethoxyphenoxy)ethyl]amino}-propyl)-2-methoxybenzenesulfonamide (yield 64%).Prior to purification by gel column chromotography, the crude product has approximately 9% (area) tamsulosin free base and approximately 73.3% (area) of the byproduct. Following purification by gel column chromotography, tamsulosin free base is not detected according to HPLC method 1 analysis.The 1H-NMR pMSO-d6, 300 MHz), delta (ppm) of the byproduct is characterized as follows: 0.94 (d, 3H, NCHCH3); 1.24 (t, 6H, OCH2CH3); 2.49 (m (overlapped with DMSO-d5), IH, Ar- CHA); 2.84 (dd, IH, Ar-CHB); 2.89-3.05 (complex signal , 5H, N(CH2-)2 and NH-CHCH3); 3.83 (s, 3H, OCH3); 3.78-4.01 (complex signal, 8H52 OCH2CH3 and 2 NHCH2CH2O); 6.79-6.94 (complex signal, 8H, Ar-H of Ar-OEt); 6.97 (broad s, 2H SO2NH2); 7.00, (d, IH, 3-H (Ar- SO2NH2)); 7.41 (dd, IH, 4-H (Ar-SO2NH2); 7.57 (d, IH, 6-H (Ar-SO2NH2));The 13C NMR (DMSO-d6, 300 MHz), delta (ppm) of the byproduct is characterized as follows: 14.9 (2CH3, 2 OCH2CH3); 15.3 (CH3, CHCH3); 38.3 (CH2 , ArCH2); 50.1 (2 CH2, 2 OCH2CH2N); 56.1 (CH3, OCH3); 59.2 (CH, CHCH3); 63.9 (2 CH2, 2OCH2CH3); 68.6 (2 CH2, 2 OCH2CH2N); 112.4 (CH, C3 (Ar-SO2NH2)); 113.6 , 113.7 and 120.9 (2 x 4CH (Ar-OEt)); 128.1 (CH, C6 (Ar-SO2NH2); 130.9 and 132.3 (2 x C, Ci and C5 (Ar-SO2NH2)); 134.3 (CH, C4 (Ar-SO2NH2); 148.4 and 148.5 2 X 2C (Ar-OEt); 154.2 (C, C2 (Ar-SO2NH2).

The basis of chemical reaction formula synthesis, the synthesis route is composed of some specific reactions and combined according to certain logical thinking. We look forward to the emergence of more reaction modes in the future.

Reference:
Patent; MEDICHEM, S.A.; WO2007/4077; (2007); A2;,
Amide – Wikipedia,
Amide – an overview | ScienceDirect Topics