7,7,8,9-tetramethyl-2-(((2 S ,3 R ,4 R )-2,3,4,5-tetrahydroxypentyl) oxy)-6,7-dihydro-3H,5H- pyrido[1,2,3-de]quinoxalin-3-one

7,7,8,9-tetramethyl-2-(((2 S ,3 R ,4 R )-2,3,4,5-tetrahydroxypentyl) oxy)-6,7-dihydro-3H,5H- pyrido[1,2,3-de]quinoxalin-3-one

4a...................

 8,9-tetramethyl-2-(((4 S ,4' R ,5 S )-2,2,2',2'-tetramethyl-[4,4'-bi(1,3- dioxolan)]-5-yl)methoxy)-6,7-dihydro-3H ,5H-pyrido[1,2,3-de]quinoxalin-3-one

Norfolk island

East of Australia, the Norfolk Ridge extends from New Caledonia to New Zealand. The central section of this north-south oriented ridge is 1,000 kilometers (600 miles) long and 70 kilometers (40 miles) wide, and is almost entirely submerged. Only the volcanic tops of Norfolk and Philip islands break the surface of the Pacific Ocean.

Norfolk Island

Territory

Norfolk Island, a tiny Australian island in the South Pacific Ocean, is defined by pine trees and jagged cliffs. Sandy beaches include Emily Bay, with reef-protected waters. Norfolk Island National Park offers views over palm forests from Mt. Pitt. In the capital Kingston, the Norfolk Island Museum traces the island's colourful past. The Kingston and Arthur's Vale Historic Area has a ruined British penal colony.

Capital: Kingston

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4,4-Dimethoxybut-1-yne

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4,4-Dimethoxybut-1-yne: 1-butyne, 4,4-dimethoxy-; 4,4-Dimethoxy-1-butyne; 4,4-Dimethoxybut-1-yne; (1) (33639-45-1)



4,4-Dimethoxybut-1-yne (1) has the following physical and spectroscopic properties: bp 62-67 °C (75 mmHg);

¹H NMR (CDCl₃, 600 MHz)
δ 2.03 (t, J = 2.7 Hz, 1 H),TRIPLE BOND H
2.53 (dd, J = 5.6, 2.7 Hz, 2 H), CH2
3.38 (s, 6 H), TWO METHOXY
4.55 (t, J = 5.6 Hz, 1 H).      O-CH-O

  

¹³C NMR (CDCl₃, 150 MHz) δ: 23.7, 53.4, 70.2, 79.3, 102.3.

HRMS (ESI) m/z: Calcd. for C₆H₁₀O₂ [M+Na]⁺: 137.0573, found: 137.0573.

IR (cm^-1): 3289, 2938, 2834, 2124, 1447, 1423, 1362, 1240, 1192, 1120, 1064.

Anal. calcd for C₆H₁₀O₂: C, 63.14; H, 8.83. Found: C, 62.86; H, 8.86.






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(3,4,5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2- dioxide hydrobromide

(3,4,5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2- dioxide hydrobromide; (2b)
 


Synthesis of substituent R² (3,4,5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2- dioxide hydrobromide; (2b) was carried out as shown in Scheme-4 and the stepwise procedure is depicted below:
Scheme-4:

Bz-NH

Substitued R² (2b)
Step-1 : 2,3-dimethylbuta-L3-diene (14)
To 2,3-dimethylbutane-2,3-diol (13, 85g), 48% aqueous HBr was added to get the colorless solution. Mixture was fractionally distilled, washed twice with water and dried over anhydrous CaCl₂. Mixture was redistilled and the fraction of 69-70 °C was collected to get 2,3-dimethylbuta-l,3-diene (14, 38g. 64%yield). 1H NMR: (CDCl₃, 400 MHz): δ 5.06 (2H, s), 4.97 (2H, s), 1.92 (6H, s); ESI-MS: (+ve mode) 83.3 (M+H)⁺ (70 %).


Step-2: 3,4-dimethyl-2,5-dihydrothiophene 1,1 -dioxide (15)
A mixture of hydroquinone (492mg) and 2,3-dimethylbuta-l ,3-diene (14, 31.96 ml) was placed in sealed tube and a solution of sulfur dioxide in MeOH (140 ml) was added. Reaction mixture was heated at 85 °C for 4 h and cooled to room temperature. Crystals obtained was filtered, washed with cold methanol and dried to get 3,4- dimethyl-2,5-dihydrothiophene 1,1 -dioxide (15) as white crystalline solid (30 gm, 72% yield).
lH NMR: (CDCl_3, 400 MHz): δ 3.73 (4H, d, J = 1.2 Hz), 1.78 (6H, t, J = 1.2 Hz); ESI- MS: (+ve mode) 147.2 (M+H)⁺ (70 %), 169.1 (M+Na)⁺ (40%).


Step-3: 3,4-bis(bromomethyl)-2,5-dihydrothiophene 1,1 -dioxide (16)
A mixture of 3,4-dimethyl-2,5-dihydrothiophene 1,1-dioxide (15, 20g), 1- bromopyrrolidine-2,5-dione (53.5g), and AIBN (400mg) in CHC1₃ was heated for 15 hr. After completion of reaction, filtrate was evaporated under reduced pressure. The residue obtained was recrystallize from methanol to get 3,4-bis(bromomethyl)-2,5- dihydrothiophene 1,1-dioxide as a white crystals (16, 19 g, 45% yield).
1H NMR: (CDC1_3> 400 MHz): δ 4.06 (4H, s), 4.01 (4H, s); ESI-MS: (+ve mode) 303.8 (M+H)⁺ (90 %), 305.7 (M+2H)⁺ (70%).


Step-4: 5-benzyl-3,4,5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2-dioxide (17)
Mixture of 3,4-bis(bromomethyl)-2,5-dihydrothiophene 1,1-dioxide (16, 12g) and phenylmethanamine (10.84ml) in acetonitrile was stirred at 25 °C for 2 hr. After completion of reaction, solvent was removed under reduced pressure, ethyl acetate and IN NaOH were added, organic layer was separated and aq layer was extracted with ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous Na₂S0₄ and concentrated under reduced pressure to give 5-benzyI-3,4,5,6-tetrahydro- lH-thieno[3,4-c]pyrrole 2,2-dioxide (17) as a solid compound (3.7 g, 38% yield).
1H NMR: (CDCI_3, 400 MHz): δ 7.34-7.29 (5H, m), 3.88 (2H, s), 3.77 (4H,s), 3.61 (4H, s); ESI-MS: (+ve mode) 250.3 (M+H)⁺ (100 %).

Step-5: benzyl 4,6-dihvdro-lH-thieno[3,4-clpyrrole-5(3H^")-carboxylate 2,2-dioxide (IS) A mixture of 5-benzyl-3,4,5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2-dioxide (17, 3.6g) and CBZ-C1 (13.5 ml) in toluene was stirred for 3 hr. After completion of reaction, diethyl ether was added till solid precipitated out. Solid was filtered and dried under reduced pressure to get benzyl 4,6-dihydro-lH-thieno[3,4-c]pyrrole-5(3H)- carboxylate 2,2-dioxide (18, 2.7 g, 64% yield). ^lH NMR: (CDC1_3, 400 MHz): δ 7.38-7.35 (5H, m), 5.19 (2H, s), 4.31 (4H, s), 3.88 (4H, d, J = 13.6 Hz); ESI-MS: (+ve mode) 294.4 (M+H)⁺ (80 %).


Step-6: 3 A5,6-tetrahydro-lH-thieno[3,4-c]pyrrole 2,2-dioxide hydrobromide (2b)
To a solution of benzyl 4,6-dihydro-lH-thieno[3,4-c]pyrrole-5(3H)-carboxylate 2,2-dioxide (18, 3.7 g) in glacial acetic acid, HBr in glacial acetic acid was added and the reaction mixture was stirred at 2 °C for 3h. After completion of reaction, diethyl ether was added to afford sticky solid, solvent was decanted and added minimum amount of methanol to get the crystalline solid as 3,4,5,6-tetrahydro-lH-thieno[3,4- c]pyrrole 2,2-dioxide hydrobromide as a hydrobromide salt (2b, 1.5 g, 50% yield). 1H NMR: (CDCI₃, 400 MHz): δ 9.43 (2H, bs), 4.08 (4H, s), 4.02 (4H, s); ESI-MS: (+ve mode) 160.4 (M+H)⁺ (88 %).


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3-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine.

5.........3-pyridylboronic acid pinacol ester
 3-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)pyridine.
 Pyridine, 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-; (329214-79-1)

compd5=  obtained the product in 74-82% yield in different runs. The product exhibits the following physical properties: mp 102-105°C; IR (KBr pellet) cm⁻¹ 2994, 2968, 2932, 1609, 1572, 1476, 1410, 1361, 1209, 1154, 1063, 1017, 953, 926, 859, 833, 800, 759, 705; ¹H NMR pdf (500 MHz, CDCl₃): δ 1.33 (s, 12H), 7.25 (ddd, J=1.1, 4.9, 7.5, 1H), 8.03 (dt, J=1.8, 7.5, 1H), 8.64 (dd, J=1.9, 4.9, 1H), 8.93 (d, J=1.1, 1H); ¹³C NMR (126 MHz, CDCl₃) δ 24.8, 84.1, 123.0, 142.2, 152.0, 155.5; MS (EI, 70 eV): 205 (M+, 46), 204 (15), 191 (12), 190 (100), 189 (25), 162 (10), 148 (44), 147 (14), 120 (18), 119 (11), 106 (100), 105 (35), 85 (15), 59 (17), 58 (19); HRMS (EI) m/z 205.1280, calcd for C₁₁H₁₆NO₂B 205.1274. Anal. Calcd for : C₁₁H₁₆BO₂N: C, 64.43; H, 7.86; N, 6.83. Found: C, 64.23; H, 7.99; N, 6.88.

An Improved Protocol for the Preparation of 3-Pyridyl- and Some Arylboronic Acids

Wenjie Li ,* Dorian P. Nelson ,* Mark S. Jensen , R. Scott Hoerrner , Dongwei Cai , Robert D. Larsen , and Paul J. Reider

Process Research Department, Merck Research Laboratories, P.O. Box 2000, Rahway, New Jersey 07065 wenjie_li@merck.com; dorian_nelson@merck.com

J. Org. Chem., 2002, 67 (15), pp 5394–5397

DOI: 10.1021/jo025792p

Publication Date (Web): June 13, 2002

Copyright © 2002 American Chemical Society

Abstract

3-Pyridylboronic acid was prepared in high yield and bulk quantity from 3-bromopyridine via a protocol of lithium−halogen exchange and “in situ quench”. This technique was further studied and evaluated on other aryl halides in the preparation of arylboronic acids. 

 paper

 http://www.orgsyn.org/demo.aspx?prep=v81p0089

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Tunis, tunisia
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 With Tarek Chelsea at Av. de la Liberté - Lafayette Tunis.


 

 
 Past... — at Carthage Land.

 

 

 

 
 


 

 

 
 

 
  Wisem Djerbien at Hay ennasr tunis.

 
 
 

 
 

 
 

 

 

 

 
 
 

 
 
 

 Les Berges du Lac, Tunis, Tunisia

 

 Alstom low-floor trolley, Place de Barcelona, Tunis, Tunisia

 

 Tunis-Carthage International Airport, Tunisia

 

 Republique Station, Metro leger, Tunis, Tunisia

 

 People walk through the town's main avenue, Avenue Habib Bourguiba.

 

 

 




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