Category: iodides-buliding-blocks

Adding a certain compound to certain chemical reactions, such as: 340825-13-0, name is 6-Iodo-3,4-dihydronaphthalen-1(2H)-one, belongs to iodides-buliding-blocks compound, can increase the reaction rate and produce products with better performance than those obtained under traditional synthetic methods. Here is a downstream synthesis route of the compound 340825-13-0, Application In Synthesis of 6-Iodo-3,4-dihydronaphthalen-1(2H)-one

A solution of 6-iodo-3,4-dihydronaphthalen-1(2B)-one (5.0 g, 18.38 minol), 4- fluorobenzenethiol (4.11 mL, 38.6 minol) and absolute ethanol (20 mL) was cooled with an ice-water bath and bubbled with HC1 gas until saturation was reached (observed by theformation of a white precipitate). The mixture was allowed to warm to rt and stirred overnight. The mixture was dissolved in ether (250 mL) and washed sequentially with water (2 x 125 mL), 0.5 M aqueous Na2CO3 (3 xlOO mL) and brine (100 mL). The organic layer was dried and concentrated to provide a solid (9.2 g) which was a mixture of thioketal and vinyl sulfide. The solid was dissolved in chloroform (150 mL) andcooled in an ice-water bath. A solution of mCPBA (35 g, 156 minol) in DCM (200 mL)was washed with brine (50 mL), dried, filtered, and the filter cake was washed with DCM(50 mL). The combined filtrates were added dropwise in portions to the chloroformsolution of the products from above until the reaction was completed as judged by LCMS(175 ml. of the mCPBA solution was needed). The mixture was cooled in an ice bath,filtered to remove the insoluble material, and the filtrate was stirred with 10% aqueousNa2S2O3 (120 mL) for 5 min. The organic phase was separated, washed sequentially with 10% aqueous Na2S2O3 (2 x 120 mL), 10% aqueous Na2CO3 (3 x 200 mL) and brine (150 mL), dried and concentrated. The residue was purified by column chromatography on silica gel, eluting with EtOAc-hexanes (gradient from 0-20%) to give 4-((4- fluorophenyl)sulfonyl)-7-iodo-1,2-dihydronaphthalene (5.3 g, 70% yield) as a white foamy solid.

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 6-Iodo-3,4-dihydronaphthalen-1(2H)-one, and friends who are interested can also refer to it.

Reference:
Patent; BRISTOL-MYERS SQUIBB COMPANY; BATT, Douglas G.; DHAR, T.G. Murali; (146 pag.)WO2018/71314; (2018); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Application of 112671-42-8, 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. 112671-42-8, name is 4-Bromo-1-iodo-2-nitrobenzene, This compound has unique chemical properties. The synthetic route is as follows.

(1) Take 21.2 g (100 mmol) of 4-dibenzofuran boronic acid,32.6g (100mmol) of 2-iodo-5-bromonitrobenzene,(1%) Pd (PPh3) 4,40g (300mmol) sodium carbonate,Toluene (800mL), ethanol (200mL) and water (200mL),Heated to reflux, reacted for 8h, the reaction was completed;The reaction solution was extracted with ethyl acetate, and the organic phase was concentrated.A yellow solid A was obtained;

The chemical industry reduces the impact on the environment during synthesis 4-Bromo-1-iodo-2-nitrobenzene. I believe this compound will play a more active role in future production and life.

Reference:
Patent; Yantai Xianhua Chemical Technology Co., Ltd.; Xing Qifeng; Feng Peichuan; Chen Yue; Hu Lingfeng; Chen Yili; (28 pag.)CN110698458; (2020); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps, and cheap raw materials. 148870-57-9, name is 7,8-Dimethoxy-3-(3-iodopropyl)-1,3-dihydro-2H-3-benzazepin-2-one, A new synthetic method of this compound is introduced below., Product Details of 148870-57-9

Based on EP 0 534 859 A solution of the (d) camphorsulphonate salt obtained in Example 4 in ethyl acetate is brought to basic pH using sodium hydroxide and then the organic phase is separated off, washed, dried over Na2SO4 and evaporated. A mixture composed of 5.6 g of potassium carbonate, 2.2 g of the above amine in 100 mL of acetone and 4 g of 3-(3-iodopropyl)-7,8-dimethoxy-1,3-dihydro-2H-3-benzazepin-2-one is then refluxed for 18 hours. The solvent is evaporated off in vacuo, and the residue is taken up in ethyl acetate and then extracted with 3N hydrochloric acid. The aqueous phase separated off is brought to basic pH using sodium hydroxide and is then extracted with ethyl acetate. After washing until neutral and drying over MgSO4, evaporation in vacuo is carried out to obtain 4.5 g of an oil which is purified on a silica column using a mixture of dichloromethane/methanol (90/10) as eluant. Yield=64%

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; LES LABORATOIRES SERVIER; CARRANZA, Maria Del Pilar; GARCIA ARANDA, Maria Isabel; GONZALEZ, Jose Lorenzo; SANCHEZ, Frederic; US2014/107334; (2014); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Some common heterocyclic compound, 19094-56-5, name is 2-Chloro-5-iodobenzoic acid, molecular formula is C7H4ClIO2, 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. Recommanded Product: 19094-56-5

Example 1 : Synthesis of the fluoride VIII.1Oxalylchloride (176kg; 1386mol; 1 ,14eq) is added to a mixture of 2-chloro-5-iodo benzoic acid (343kg; 1214mol) (compound IX.1 ), fluorobenzene (858kg) and N,N- dimethylformamide (2kg) within 3 hours at a temperature in the range from about 25 to 30C (gas formation). After completion of the addition, the reaction mixture is stirred for additional 2 hours at a temperature of about 25 to 30C. The solvent (291 kg) is distilled off at a temperature between 40 and 45C (p=200mbar). Then the reaction solution (91 1 kg) is added to aluminiumchloride AICI3 (181 kg) andfluorobenzene (192kg) at a temperature between about 25 and 30C within 2 hours. The reaction solution is stirred at the same temperature for about an additional hour. Then the reaction mixture is added to an amount of 570 kg of water within about 2 hours at a temperature between about 20 and 30C and stirred for an additional hour. After phase separation the organic phase (1200kg) is separated into two halves (600kg each). From the first half of the organic phase solvent (172kg) is distilled off at a temperature of about 40 to 50C (p=200mbar). Then 2-propanole (640kg) is added. The solution is heated to about 50C and then filtered through a charcoal cartouche (clear filtration). The cartouche may be exchanged during filtration and washed with a fluorobenzene/2-propanole mixture (1 :4; 40kg) after filtration. Solvent (721 kg) is distilled off at a temperature of about 40 to 50C and p=200mbar. Then 2-propanole (240kg) is added at a temperature in the range between about 40 to 50C. If the content of fluorobenzene is greater than 1 % as determined via GC, another 140kg of solvent are distilled off and 2-propanole (140kg) is added. Then the solution is cooled from about 50C to 40C within one hour and seeding crystals (50g) are added. The solution is further cooled from about 40C to 20C within 2 hours. Water (450kg) is added at about 20C within 1 hour and the suspension is stirred at about 20C for an additional hour before the suspension is filtered. The filter cake is washed with 2-propanole/water (1 :1 ; 800kg). The product is dried until a water level of <0.06%w/w is obtained. The second half of the organic phase is processed identically. A total of 410kg (94%yield) of product which has a white to off-white crystalline appearance, is obtained. The identity of the product is determined via infrared spectrometry. These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 19094-56-5, its application will become more common. Reference:
Patent; BOEHRINGER INGELHEIM INTERNATIONAL GMBH; WEBER, Dirk; RENNER, Svenja; FIEDLER, Tobias; ORLICH, Simone; WO2011/39107; (2011); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Researchers who often do experiments know that organic synthesis is a process of preparing more complex target molecules from simple raw materials through one or more chemical reactions. Generally, it requires fewer steps, and cheap raw materials. 289039-83-4, name is Methyl 2-amino-5-bromo-3-iodobenzoate, A new synthetic method of this compound is introduced below., name: Methyl 2-amino-5-bromo-3-iodobenzoate

To a solution of methyl 2-amino-5-bromo-3-iodobenzoate (7.47 g, 20.99 mmol) in TEA (40 mL, 287 mmol) is added Pd(PPh3)2C12 (0.884 g, 1 .259 mmol), and copper(l) iodide (0.240 g, 1.259 mmol). The mixture is stirred under N2 for about 5 mm, and then trimethylsilylacetylene (3.83 mL, 27.3 mmol) is added. The mixture is stirred at rt for I h. The reaction is followed by LCMS (only 6% product after I h). The mixture is then transferred to a pressure tube and additional Pd(PPh3)2C12 (0.14 g, 0.199 mmol) and copper(l) iodide (0.036 g, 0.189 mmol) are added. The mixture is purged with N2 for 1 mm, and then it is heated at 60 C for 2 h (LCMS shows 54% mono-alkyne and 35% bis-alkyne). The reaction mixture is concentrated under reduced pressure. The residue is taken up in CH2CI2 and filtered through a plug of Celite. The Celite plug is washed with CH2CI2. The filtrate is washed with water (2x) and brine (lx), dried over Na2SO4, filtered and concentrated. The residue is chromatographed over silica gel (120 g ISCO column) eluting with 0-5% EtOAc/hexane gradient to yield a mixture of methyl 2-amino-5- bromo-3-((trimethylsilyl)ethynyl)benzoate and methyl 2-amino-3, 5- bis((trimethylsilyl)ethynyl)benzoate (4.2 to I ratio by I H NMR). LCMS (ES API) MH+ = 326 & 328 for Br isotopes mono-alkyne product; and LCMS (ES API) MH+ = 344 bis-alkyne product.A mixture of methyl 2-amino-5-bromo-3-((trimethylsilyl)ethynyl)benzoate (500 mg, 1 .53mmol; contaminated with 20% of methyl 2-amino-3,5-bis((trimethylsilyl)ethynyl)benzoate) and2 eq of Cul (584 mg, 3.07 mmol) in DMF (4 mL) is set under N2 and heated in a sealed tube at100 C for 80 mm. Upon cooling, the reaction mixture is diluted with Et20 and filtered through aplug of Celite. The Celite plug is washed with Et20 and EtOAc. The filtrate is concentrated underreduced pressure. The residue is chromatographed over silica gel eluting with 0-15% EtOAchexane gradient to give the title compound as a light yellow solid. LCMS (ES API) MH+ = 254 &256 for Br isotopes.

The synthetic route of 289039-83-4 has been constantly updated, and we look forward to future research findings.

Reference:
Patent; GLAXOSMITHKLINE INTELLECTUAL PROPERTY (NO.2) LIMITED; BECHERER, J. David; CADILLA, Rodolfo; DEATON, David Norman; HAFFNER, Curt; HENKE, Brad Richard; PREUGSCHAT, Frank; SCHULTE, Christie; (69 pag.)WO2016/87975; (2016); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Synthetic Route of 116632-39-4, 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. 116632-39-4, name is 5-Bromo-2-iodotoluene belongs to iodides-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.

Apparatus set-up: (0416) A 10 L 3 -necked round-bottomed flask, equipped with a mechanical overhead stirrer, reflux condenser, nitrogen inlet and exhaust. (0417) Experimental Procedure: (0418) Intermediate 3 (200 g, 0.644 mol) and intermediate 4 (190.9 g, 0.644 mol) were taken in 1, 2-dimethoxy ethane (2 L). (0419) Sodium carbonate solution (136.5 g, 1.288 mol, dissolved in 1 L of water) was added. (0420) The reaction mixture was degassed with nitrogen for an hour. (0421) Pd(PPh3)4 (7.44 g, 0.00644 mol) was added and heated at 100 C for 18 h. (0422) After completion of the reaction, it was filtered through a Florosil-silica plug and concentrated. (0423) The residue was dissolved in ethyl acetate (2 L), washed with water (1 L), brine (1 L), dried over sodium sulphate and concentrated. The crude product (200 g) was purified by silica column chromatography using hexane as an eluent to get 160 g of Intermediate D with 93 % HPLC purity. (0424) It was again purified by hot acetonitrile crystallization to get 135 g of Intermediate D with 97 % HPLC purity. (0425) It was further purified by hot acetonitrile crystallization to get 130 g of Intermediate D with 98.22 % HPLC purity. (0426) 130 g of Intermediate D at 98.22 % HPLC purity was crystallized with hot ethyl acetate/ methanol (1: 1.5) to get 100 g of Intermediate D with 98.9 % HPLC purity. (0427) 100 g of Intermediate D at 98.9 % HPLC purity was crystallized with hot ethyl acetate/ methanol (1: 1) to get 60 g of Intermediate D with 99.79 % HPLC purity. (0428) Filtrate obtained from all the above crystallizations were combined and concentrated to get 55 g at 97.2 % HPLC purity. (0429) 55 g of Intermediate D 97.2 % HPLC purity was crystallized with hot ethyl acetate/ methanol (1:0.8) to get 24 g of Intermediate D with 99.81 % HPLC purity. (0430) 24 g of Intermediate D at 99.81 % purity and 60 g of 99.79 % purity were combined, dissolved in dichloromethane (500 mL), heated to 45 C, filtered the hot solution and concentrated to get 80.5 g of Intermediate D with 99.70 % HPLC purity as white solid. (0431) ^-NMR (400 MHz, COCh): delta [ppm] 2.31 (s, 3H), 7.21 (d, / = 8.00 Hz, 1H), 7.40-7.45 (m, 2H), 7.48-7.52 (m, 3H), 7.89-7.91 (m, 2H), 8.07 (s, 1H), 8.15-8.17 (m, 1H).

The synthetic route of 5-Bromo-2-iodotoluene has been constantly updated, and we look forward to future research findings.

Reference:
Patent; CAMBRIDGE DISPLAY TECHNOLOGY LIMITED; SUMITOMO CHEMICAL CO., LTD; HUMPHRIES, Martin; TARRAN, William; KAMTEKAR, Kiran; STACKHOUSE, Philip; LEE, James; (76 pag.)WO2017/153731; (2017); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

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. 19099-54-8, name is 1-Iodo-2-isopropylbenzene, This compound has unique chemical properties. The synthetic route is as follows., HPLC of Formula: C9H11I

0.3 mmol of sodium carbonate and 0.1 mmol of 1,2-bis(4-methoxyphenyl)acetylene,Tetrakis(triphenylphosphine palladium) 0.005 mmol, bis(2-diphenylphosphinophenyl)ether 0.005 mmol,0.2 mmol of (3-fluoro-4-methyl)phenyl)boronic acid, 0.3 mmol of 2-isopropyliodobenzene, and 1 mL of N,N-dimethylformamide were added to a 15 mL reaction tube.Nitrogen was repeatedly filled 10 times, placed in an oil bath at 120 C, and reacted for 24 hours;Cooled to room temperature, the reaction was diluted with ethyl acetate, washed with water three times, the organic phase dried over anhydrous Na2SO4, filtered, and concentratedPurification by thin layer chromatography to give 29.4mg of the desired product, yield 63%.

According to the analysis of related databases, 19099-54-8, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Huaqiao University; Cheng Guolin; Lv Weiwei; (20 pag.)CN109879713; (2019); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Some common heterocyclic compound, 624-75-9, name is 2-Iodoacetonitrile, molecular formula is C2H2IN, 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. Recommanded Product: 2-Iodoacetonitrile

The compound obtained in Example 21 (4.6 g, 15.35 mmol) and potassium carbonate (10.6 g, 76.73 mmol) were added to acetone (100 mL) and refluxed for 2 hours by heating. To this reaction mixture was dropwise added iodoacetonitrile (1.34 mL, 18.42 mmol), and refluxed over 2 hours. The acetone was removed by vacuum distillation, and to the residue were added water (200 mL) and ethyl acetate (200 mL). The organic layer was dried over anhydrous magnesium sulfate and distillated in a vacuum. The concentrate was subjected to column chromatography (silica gel, ethyl acetate-hexane 2:3 v/v) to afford a mixture of 2:1 of [4-(2-chloropyridin-4-yl)-3-(3-methoxy-5-methylphenyl)-1H-pyrazol-1-yl]acetonitrile and [4-(2-chloropyridin-4-yl)-5-(3-methoxy-5-methylphenyl)-1H-pyrazol-1-yl]acetonitrile as yellow oil. These two regioisomers (4.78 g, 92%) were used in the next reaction step without separation.[4-(2-Chloropyridin-4-yl)-3-(3-methoxy-5-methylphenyl)-1H-pyrazol-1-yl]acetonitrile: 1H NMR (CDCl3) delta 2.29 (s, 3H), 3.71 (s, 3H), 5.19 (s, 2H), 6.73 (s, 1H), 6.75 (s, 1H), 6.85 (s, 1H), 7.06 (d, J=4.4 Hz, 1H), 7.26 (s, 1H), 7.79 (s, 1H), 8.24 (d, J=4.8 Hz, 1H); 13C NMR (CDCl3) delta 21.53, 39.97, 55.29, 110.91, 111.12, 113.65, 115.67, 118.75, 121.59, 121.65, 122.78, 130.58, 132.37, 140.16, 143.28, 149.68, 151.45, 151.79, 159.71, 162.33.[4-(2-Chloropyridin-4-yl)-5-(3-methoxy-5-methylphenyl)-1H-pyrazol-1-yl]acetonitrile: 1H NMR (CDCl3) delta 2.39 (s, 3H), 3.83 (s, 3H), 4.94 (s, 2H), 6.63 (s, 1H), 6.74 (s, 1H), 6.92-6.96 (m, 2H), 7.19 (s, 1H), 7.93 (s, 1H), 8.17 (d, J=5.2 Hz, 1H); 13C NMR (CDCl3) delta 21.56, 37.78, 55.48, 112.15, 113.91, 117.08, 118.16, 119.88, 121.36, 122.48, 128.46, 139.57, 141.60, 142.19, 142.85, 149.78, 151.95, 160.48.To a solvent mixture of THF and water (4:1, 10 mL) were added the mixture prepared in Example 22 (100 mg, 0.30 mmol), phenylboronic acid (43.9 mg, 0.36 mmol), dichlorobis(triphenylphosphine)palladium (II) (11 mg, 0.02 mmol) and potassium carbonate (42 mg, 0.30 mmol), and stirred at 70 C. for 12 hours under nitrogen atmosphere. The reaction mixture was cooled at room temperature, washed with ice water (100 mL) and extracted with ethyl acetate (100 mL×3). The organic extract was dried over anhydrous magnesium sulfate and distilled under vacuum. The residue was subjected to prep-TLC using a solvent mixture of ethyl acetate/hexane to purify the desired products.Purification yield by prep-TLC (silica gel, ethyl acetate-hexane, 1:3, v/v): (70 mg, 62%); m.p. 51-52 C.; 1H NMR (CDCl3) delta 2.41 (s, 3H), 3.81 (s, 3H), 4.95 (s, 2H), 6.76 (s, 1H), 6.82 (s, 1H), 6.95 (s, 1H), 7.06 (d, J=4.5 Hz, 1H), 7.41-7.44 (m, 3H), 7.58 (s, 1H), 7.80 (d, J=6.3 Hz, 2H), 8.01 (s, 1H), 8.53 (d, J=4.8 Hz, 1H) 13C NMR (CDCl3) delta 21.57, 37.76, 55.49, 112.31, 114.07, 116.90, 118.29, 119.60, 119.70, 122.75, 126.83, 128.71, 129.03, 129.11, 139.21, 139.61, 140.45, 141.47, 141.89, 149.88, 157.70, 160.51.

These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 624-75-9, its application will become more common.

Reference:
Patent; LEE, So Ha; Yoo, Kyung Ho; Oh, Chang Hyun; Han, Dong Keun; El-Deeb, Ibrahim Mustafa; Park, Byung Sun; Jung, Su Jin; US2011/15395; (2011); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Reference of 26059-40-5, In the chemical reaction process, reaction time, type of solvent, can easily affect the result of the reaction, thereby determining the yield and properties of the reaction product. An updated downstream synthesis route of 26059-40-5 as follows.

General procedure: A magnetic stirring bar, 2-iodobenzyl alcohol (1a, 116.0 mg, 0.5 mmol), NEt3 (251.6 mg, 2.5 mmol), and MeCN (10 mL) were placed in a stainless steel autoclave equipped with an inserted Pyrex glass liner. The autoclave was closed, purged three times with carbon monoxide, pressurized with 65 atm of CO and then heated at 250 C by salt bath with stirring for 16 h. After the reaction, excess CO was discharged at room temperature. The solvent was removed under reduced pressure, and the residue was purified by flash chromatography on silica gel (hexane/EtOAc = 3/1) to give 2a (60.4 mg, 91%) as a white solid.

According to the analysis of related databases, 26059-40-5, the application of this compound in the production field has become more and more popular.

Reference:
Article; Fukuyama, Takahide; Bando, Takanobu; Ryu, Ilhyong; Synthesis; vol. 50; 15; (2018); p. 3015 – 3021;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

Electric Literature of 63279-58-3, 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. 63279-58-3 name is 1-Bromo-4-iodonaphthalene, 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.

General Procedure I-AAThe mixture of 1-bromo-4-iodonaphthalene (I-IVb) (6.00 g, 18.01 mmol), 4-methoxyphenylboronic acid (2.74 g, 18.01 mmol), Na2CO3 (3.82 g, 36.02 mmol) and Pd(dppf)Cl2 (658 mg, 0.90 mmol) in 50 mL of THF and 10 mL of H2O was heated to reflux under argon overnight. The mixture was concentrated, the residue was partitioned between H2O and DCM, the aqueous phase was extracted with DCM. The combined organic layer was washed with brine, dried over Na2SO4, and concentrated. The residue was purified by chromatography on silica gel to afford 1-bromo-4-(4-methoxyphenyl)naphthalene (I-IVd) (4.50 g, yield 63percent).

At the same time, in my other blogs, there are other synthetic methods of this type of compound, 1-Bromo-4-iodonaphthalene, and friends who are interested can also refer to it.

Reference:
Patent; InterMune, Inc.; US2011/152246; (2011); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com