Month: November 2020

77317-55-6, These common heterocyclic compound, 77317-55-6, name is Methyl 2-amino-5-iodobenzoate, 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: CuCl (1.50 mg, 0.0150 mmol), DPEPhos (8.10 mg, 0.0150 mmol) and KOt-Bu (1.70 mg,0.0150 mmol) were added to a 8 mL vial charged with a magnetic bar. The vial was sealedwith a cap (phenolic open top cap with gray PTFE/silicone) and purged by N2 gas for 5 min.Toluene (0.8 mL) and methyl 2-aminobenzoate (1a) (46.6 L, 0.360 mmol) were added to themixture, which was allowed for 10 min. And then a solution of phenyl vinyl sulfone (2) (50.5mg, 0.300 mmol) in toluene (0.7 mL) was added to the reaction solution. After stirring atroom temperature for 5 h, THF (5 mL) was added and the reaction was allowed to cool to 0C (ice bath). After addition of KOt-Bu (101 mg, 0.900 mmol), the resulting solution wasallowed to stir for further 1 h at 0 C. After that time, the reaction was quenched with asaturated aqueous solution of NH4Cl (1 mL) and NaHCO3 (2 mL) and washed with EtOAc (7x 3 mL). The organic layers were combined, dried over MgSO4, filtered, and concentrated invacuo. The crude product was purified by silica gel column chromatography (CH2Cl2/EtOAc,8:1) to afford the desired product 4a (76.8 mg, 0.267 mmol, 89% yield) as a yellow solid.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 77317-55-6.

Reference:
Article; Kang, Seongil; Yoon, Hongju; Lee, Yunmi; Chemistry Letters; vol. 45; 12; (2016); p. 1356 – 1358;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

452-68-6, These common heterocyclic compound, 452-68-6, name is 1-Fluoro-4-iodo-2-methylbenzene, 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 9 Ethyl Z-(1R’,3S’)-3-(4-fluoro-3-methylphenyl)-2-[3-(5-methyl-2-m-tolyloxazol-4-yl-methoxy)cyclohexyloxymethyl]acrylate 220 mg of tetrabutylammonium chloride and 332 mg of potassium carbonate are suspended in 4 ml of dimethylformamide and stirred intensively for 20 min. 400 mg of ethyl (1R,3S)-2-[3-(5-methyl-2-m-tolyloxazol-4-ylmethoxy)cyclohexyloxy-methyl ]acrylate, 25 mg of triphenylphosphine and 212 mg of 4-fluoro-3-methyliodo-benzene are added, the mixture is degassed and vented with argon and 10 mg of palladium acetate and 0.2 mol of water are added. The mixture is heated at 60 C for 4 h. After cooling, 20 ml of ethyl acetate and 50 ml of sat. NaCI solution are added. The organic phase is dried over sodium sulfate, the solvent is removed under reduced pressure and the residue is purified by flash chromatography on silica gel (n-heptane/ethyl acetate=4:1). This gives ethyl Z-(1R’,3S’)-3-(4-fluoro-3-methylphenyl)-2-[3-(5-methyl-2-m-tolyloxazol-4-ylmethoxy)cyclohexyloxymethyl ]-acrylate as a colorless oil. C31H38FNO5 (523.65), MS (ESI): 524 (M+H+).

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 452-68-6.

Reference:
Patent; Aventis Pharma Deutschland GmbH; US2004/209920; (2004); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

628-21-7, Adding a certain compound to certain chemical reactions, such as: 628-21-7, name is 1,4-Diiodobutane, 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 628-21-7.

2-[4-(4-iodobutoxy)phenyl]-1,2-benzisoselenazol-3(2H)-one (Compound 14) To a suspension of NaH (60% emulsion washed with pentane and dried in vacuo, 60 mg, 1.50 mmol) in dry DMF (1 mL) at 0 C. under argon was added a solution of 13 (300 mg, 1.03 mmol) in dry DMF (7 mL) under argon via a cannula. The resultant solution was stirred for 2 hours at room temperature then added via a cannula to a solution of 1,4-diiodobutane (3.20 g, 10.3 mmol) in dry DMF (2 mL) under argon. The resultant solution was stirred in the dark for 2 days at room temperature under argon. Water (1 mL) was carefully added and solvent removed in vacuo to give an oily residue. The residue was dissolved in CH2Cl2 (20 mL) and the organic phase washed with H2O (20 mL), 10% Na2S2O3 (20 mL), and H2O (20 mL). The organic extract was dried over Na2SO4 and filtered. Solvent was removed from the filtrate in vacuo, giving a yellow oily residue. The residue was chromatographed (silica gel packed in CH2Cl2, eluding with 19:1 CH2Cl2/diethyl ether) and fractions containing product were combined. Solvent was removed in vacuo, giving sufficiently pure 14 as a white solid (254 mg, 52%). 1H NMR (299.9 MHz, CDCl3) delta 8.11 (d, J=7.8 Hz, 2H, ArH), 7.68-7.62 (m, 2H, Ar-H), 7.52-7.43 (m, 3H, Ar-H), 6.94 (d, J=9 Hz, 2H, Ar-H), 4.02 (t, J=5.9 Hz, 2H, -O-CH2-), 3.27 (t, J=6.6 Hz, 2H, -CH2-I), 1.98 (m, 4H, -CH2-CH2-); 13C-NMR (125.7 MHz, CDCl3) delta 166.20 (carbonyl), 158.0 (aromatic), 138.12 (aromatic), 132.73 (aromatic), 132.03 (aromatic), 129.73 (aromatic), 127.73 (protonated aromatic), 127.60 (aromatic), 126.85 (aromatic), 126.85 (aromatic), 124.08 (aromatic), 115.41 (protonated aromatic), 67.32 (-O-CH2-), 30.43 (methylene), 6.64 (-CH2-I); LRAPCI MS (+formic acid) Calcd. For C17H17NOSeI: 473, found: 473.

According to the analysis of related databases, 628-21-7, the application of this compound in the production field has become more and more popular.

Reference:
Patent; Medical Research Council; University of Otago; US2004/29851; (2004); A1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

19230-28-5, 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. 19230-28-5, name is 1,3-Dichloro-2-iodobenzene, A new synthetic method of this compound is introduced below.

Preparation 2 Preparation of 2′,6′-Dichloro-4-biphenylcarboxylic acid A mixture of 2,6-dichloro-1-iodobenzene (0.5 g, 1.8 mmol), 4-carboxybenzeneboronic acid (0.3 g, 1.8 mmol), tetrakis(triphenylphosphine)-palladium(0) (40 mg), and sodium carbonate (0.68 g, 6.4 mmol) in a 1:1 mixture of 1,2-dimethoxyethane and water (26 mL) was heated at reflux for 16 h. The mixture was cooled and extracted with ether. The aqueous phase was acidified with 3M hydrochloric acid, allowed to stand for 16 h, and filtered. The filter cake was washed with water and dried to give the title compound.

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; SMITHKLINE BEECHAM CORPORATION; EP1140072; (2004); B1;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

6414-69-3, Adding some certain compound to certain chemical reactions, such as: 6414-69-3, name is Ethyl 3-iodopropanoate, 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 6414-69-3.

EXAMPLE VI Ethyl 2-Carboethoxy-3-indolepropanoate Ethyl 2-indolecarboxylate (3 gm), ethyl 3-iodopropanoate (5.4 gm), potassium carbonate (5 gm), and acetonitrile (50 ml) were combined and the mixture heated to reflux for 48 hours. The mixture was cooled and poured into water (50 ml). The mixture was extracted with ether (3*75 ml) and the combined ether extracts were washed with water (3*30 ml). The organic layer was dried over sodium sulfate and the solvent removed on a rotary evaporator. The diester product was obtained as a colorless oil.

Chemical properties determine the actual use. Each compound has specific chemical properties and uses. We look forward to more synthetic routes in the future to expand reaction routes of 6414-69-3.

Reference:
Patent; C.D. Searle & Co.; US5137910; (1992); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

19094-56-5, Name is 2-Chloro-5-iodobenzoic acid, 19094-56-5, belongs to iodides-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.

5-Iodo-2-chlorobenzoic acid (20.0 g, 0.071 mol) was added to a solution of 2.0 M oxalyl chloride in dichloromethane (39 ml, 0.078 mol), stirred for suspension, and then 8 drops of DMF solution was added dropwise. After the reaction was carried out for 3 hours, the solution was clarified and the reaction was almost complete. The solvent was spin-dried on a rotary evaporator, then 15 ml of methylene chloride was added, and the solvent was dried. After spin-drying, add 30 ml of dichloromethane, stir, cool to 0-5 C, add fluorobenzene (7. lg, 0.074 mol), add anhydrous aluminum trichloride (9.9 g, 0.074 mol) in batches, control The temperature is not more than 5 C, after the completion of the addition, stirring is continued at 4 C for 1 h, the reaction is almost complete by TLC, the reaction is quenched on ice-water mixture, the organic phase is separated, and the aqueous phase is extracted with dichloromethane. The phase was washed twice with 1 mol/L hydrochloric acid, washed once with water, and washed twice with 1 mol/L NaOH solution.The mixture was washed twice with saturated sodium chloride and dried over anhydrous sodium sulfate. Drain filtration, spin dry solvent to obtain oilAfter column chromatography, 20. 1g (78.6%) of a white solid was obtained.

Statistics shows that 2-Chloro-5-iodobenzoic acid is playing an increasingly important role. we look forward to future research findings about 19094-56-5.

Reference:
Patent; Huarun Shuang He Pharmaceutical Co., Ltd.; Zhai Jianguo; He Yang; Zhu Yingjie; Zhou Yisui; Ma Hongmin; Song Meng; (46 pag.)CN108218928; (2018); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

108078-14-4, 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. 108078-14-4, name is 2-Iodo-3-methylbenzoic acid, A new synthetic method of this compound is introduced below.

BEAD LOADING Rink Amide MBHA resin (87 mg, 0.06 mmol, 0.69 mmol/g loading) was pre-swelled in a 5 mL disposable syringe equipped with a frit by rotating with DCM (3 mL) for 1 h. The resin was then washed with DMF (5 X 4 mL). The Fmoc protecting group on the bead was removed by treatment with 5 bed volumes (ca. 4 mL) of a 20% piperidine solution in DMF for 20 min. Meanwhile, Fmoc-Phe-OH (116 mg, 0.3 mmol, 5 equiv) was dissolved in DMF (3 mL) along with HOBt (41 mg, 0.3 mmol, 5 equiv). Diisopropyl carbodiimide (DIC) (50 muL, 0.3 mmol, 5 equiv) was then added and the resulting mixture was stirred at room temperature for 20 min. After 20 minutes, the resin was washed with DMF (5 X 4 mL). To the thoroughly washed resin bed, was added the coupling solution (Fmoc-Phe-OH,HOBt, and DIC), and the resulting mixture was rotated for 12 h. The loaded resin was then washed with DMF (5 X 4 mL) and used in subsequent Fmoc solid phase peptide synthesis as described below. FMOC REMOVAL The Fmoc group of the terminal amino acid of the growing peptide chain was deprotected by treating the resin beads (0.69 mmol/g loading) with a 20% solution of piperidine in DMF (ca. 4 mL) with rotation for three minutes. The deprotection cocktail was then discharged from the syringe and the resin beads were treated with a fresh portion of 20% piperidine in DMF for three minutes.This protocol is repeated until the resin beads have been treated with four aliquots of 20% piperidine in DMF. The final portion is then discharged from the syringe and the deprotected beads are washed with DMF (5 X 4 mL). The washed, deprotected resin beads were then immediately coupled with the next amino acid in the sequence. HOBT-MEDIATED COUPLING The next amino acid in a desired sequence was activated as the HOBt ester by dissolving the desired amino acid (0.3 mmol, 5 equivalents relative to the 0.69 mmol/g resin loading) along with HOBt (41 mg, 0.3 mmol, 5 equiv) in DMF/DCM (1:1) (3 mL). To the resulting solution was added DIC (50 muL, 0.3mmol, 5 equiv) and the resulting solution was stirred at room temperature for twenty minutes (usually while the terminal amino acid of the resin bound sequence is deprotected).The resulting solution of HOBt ester was added to the N-terminal deprotected, resin-bound, peptide sequence and the mixture was rotated for one hour. The resin beads were then thoroughly washed with DMF (5 X 4 mL). The resulting N-terminal, Fmoc-protected, resin-bound peptide sequence was then resubjected to the Fmoc removal protocol and subsequent HOBt couplings until the desired sequence had been assembled. N-TERMINAL O-IODOBENZOATE CAPPING The N-terminus of the peptide was capped with the o-iodoarylamido active site by the HOBt active ester methodology. The o-iodobenzoic acid (0.3 mmol, 5 equivalents relative to the 0.69 mmol/g resin loading) was dissolved along with HOBt (41 mg, 0.3 mmol, 5 equiv) in DMF/DCM (1:1) (3 mL). To the resulting solution was added DIC (50 muL, 0.3 mmol, 5 equiv) and the resulting solution was stirred at room temperature for twenty minutes (usually while the terminal aminoacid of the resin bound sequence is deprotected).The resulting solution of HOBt ester was added to the N-terminal deprotected, resin-bound, peptide sequence and the mixture was rotated for one hour. The resin beads were then thoroughly washed with DMF (5 X 4 mL). TFA CLEAVAGE/GLOBAL SIDE-CHAIN DEPROTECTION OF PEPTIDES Peptides were cleaved from the resin beads by employing the following protocol: The fully assembled, resin-bound peptides were prepared for cleavage by washing the beads with DMF (5 X 4 mL), DCM (5 X 4 mL), and methanol (5 X 4mL). The syringe plunger was removed from the barrel and the resin beads were dried overnight in the vacuum oven at 25 C. The following day, the resin was treated with a cleavage cocktail comprised of a mixture of TFA/H2O/TIS(95:2.5:2.5) (3 mL) for 2.5 h with minimal, intermittent agitation. The cleavage cocktail, containing the solvated, resin-free peptide was then ejected into a 5 mL pear-shaped flask and the solvent was removed under a stream of nitrogen to give a thick oil. The crude peptide was then precipitated by the addition of ice-cold diethyl ether. The solid peptide was then isolated by vacuum filtration and washed with copious amounts (ca. 15-20 mL) of cold ethyl ether. The solid peptide was then dried in vacuo. The identity of the desired sequence was verified by MALDI-TOF mass spectrometry.

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; Whitehead, Daniel C.; Fhaner, Matthew; Borhan, Babak; Tetrahedron Letters; vol. 52; 18; (2011); p. 2288 – 2291;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

A common compound: 35453-19-1, name is 5-Amino-2,4,6-triiodoisophthalic acid, belongs to iodides-buliding-blocks compound, it can change the direction of chemical reaction, and react with certain compounds to generate new functional products. A new synthetic method of this compound is introduced below. 35453-19-1

A. Preparation of 5-Amino-2,4,6-triiodoisophthaloyl Chloride (2) STR1 5-Amino-2,4,6-triiodoisophthalic acid (6.73 Kg, 12.04 mol) 1 was charged and EtOAc was added. SOCl2 (5.73 Kg, 48.17 mol) was added to the slurry in one portion and the mixture was heated at reflux for 4 hours. After the reaction, 24.2 L of unreacted SOCl2 and the solvent were distilled (64-77, 7 hrs. distillation time). The product started to precipitate when the reaction solution cooled to 55; the slurry was stirred overnight, allowing it to cool to room temperature. The solids were collected, washed with cold EtOAc (5, 3.8 L), suction-dried for 3 hours and air-dried at room temperature to give the desired product 2 (3.525 kg, 49.2% yield). The filtrate (about 25 L) was distilled to a volume of 15 L and cooled to 2 overnight. The precipitated product was collected, washed with cold EtOAc (5, 1.5 L), suction-dried and air-dried to give a second crop of the product 2 (0.83 kg, 11.6% yield). The two crops of the product were combined, 4.355 kg (60.8% yield). The product showed one spot by tlc analysis (C6 H5 CH3 /CH3 OH; 9/1).

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, 35453-19-1, other downstream synthetic routes, hurry up and to see.

Reference:
Patent; Mallinckrodt, Inc.; US4396598; (1983); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

83863-33-6, 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. 83863-33-6, name is 5-Iodo-2-methylaniline, This compound has unique chemical properties. The synthetic route is as follows.

PREPARATION 21 N-(4-Iodo-2-methylphenyl)acetamide In the manner of Preparation 5, 10 g (0.043 mol) of 5-iodo-2-methylaniline was converted into the title compound: yield 11.1 g (94%); m.p. 182-183 C. Analysis calculated for C9 H10 INO: C, 39.29; H, 3.66; N, 5.09%. Found: C, 39.61; H, 3.77; N, 4.96%.

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; Pfizer Inc.; US4762838; (1988); A;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com

18698-96-9, name is 2-(2-Iodophenyl)acetic acid, belongs to iodides-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. 18698-96-9

(1-bis) A suspension of 2-iodophenyl acetic acid (Ig, 3.82 mmol), 4-bromobenzenethiol (0.722 g, 3.82 mmol), KOH (0.427 g, 7.63 mmol) and copper powder (24 mg, 0.38 mmol) in 2 mL of water, was allowed to react in microwave(conditions: 2x 6 min, 180 W, T max=100¡ãC, P max=100 psi) .The suspension obtained was dissolved in 2N aqueous solution of KOH and then filtered. The filtrate was acidified with IN aq. HCl; the white precipitate was filtered, dried in vacuo, purified by trituration with acetone to give the pure acid 1-bis as white solid (l.ldeltag, 94percent) .1H-NMR (CDCl3, 200MHz): 7.44 (d, J= 7Hz, IH); 7.36-7.26 (m, 5H); 7.01 (d, J= 8.4Hz, 2H); 3.86 (s, 2H). Anal. Calcd. for Ci4H11BrO2S (MW=323.2): C 52.03; H 3.43; Br 24.72; O 9.90; S 9.92.; Example 62- (2-biphenyl-4-ylthio) phenyl) acetic acid (19a), 2- (2- (4- methoxyphenylthio) phenyl) acetic acid (19b), 2- (2-biphenyl-4- ylthio) phenyl) -N-hydroxyacetamide (21a), N-hydroxy-2- (2- (4- methoxyphenylthio) phenyl) acetamide (21b) and 2- (2- (4- (but-2- iniloxy) phenylthio) phenyl) -N-hydroxyacetamide (21c); (16) Compound 16 was synthesized according to the procedure described for the preparation of 10, starting from o-iodophenylacetic acid (5 g, 19.08 mmol) and 4- bromobenzenethiol (2.4 g, 19.08 mmol) into 5 portions of 1 g each. The obtained suspension was collected and diluted in KOH 2N. The obtained suspension was filtered and acidified with HCl IN. The formed precipitate was brought to dryness under reduced pressure at 500C. There were recovered 4.37 g of 16 (88percent, white solid) . 1H-NMR (de-DMSO, 200MHz ) : 3 . 74 ( s , 2H) , 7 . 07 (d, J=8Hz , 2H) , 7 . 30 -7 . 42 (m, 4H) 7 . 4 9 (d, J=8Hz , 2H) , 12 . 34 (br . s , IH) .

Statistics shows that 18698-96-9 is playing an increasingly important role. we look forward to future research findings about 2-(2-Iodophenyl)acetic acid.

Reference:
Patent; BRACCO IMAGING SPA; UNIVERSITA DI PISA; WO2008/15139; (2008); A2;,
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com