4330-21-6

Basic information

• Product Name: 2-Deoxy-alpha-D-erythropentofuranosyl chloride 3,5-bis(4-methylbenzoate)
• Synonyms: 1-Chloro-2-deoxy-3,5-di-O-(4-toluoyl)-alpha-D-ribofuranose;α-D-erythro-Pentofuranosylchloride, 2-deoxy-, 3,5-bis(4-Methylbenzoate);3,5-bis(toluoyl)-2-deoxyribosyl chloride;1-α-Chloro-3,5-di-O-(4-toluoyl) -2-deoxy-D-ribofuranose;1-CHLORO-3,5-BIS[O-(4-TOLUOYL)]-2-DEOXYRIBOSE;3,5-DI-O-(P-TOLUYL)-2-DEOXY-ALPHA-D-RIBOFURANOSYL CHLORIDE;3,5-di-O-(P-toluyl)-2-deoxy-D-*ribofuranosyl chlo;2-deoxydi(p-toluoyl)-alpha-D-erythro-pentofuranosyl chloride
• CAS NO: 4330-21-6
• Molecular Formula: C₂₁H₂₁ClO₅
• Molecular Weight: 388.84
• EINECS: 224-367-3
• Product Categories: Carbohydrates;Carbohydrates A to;Carbohydrates D-FBiochemicals and Reagents;Monosaccharide
• Mol File: 4330-21-6.mol
• Article Data: 25

Chemical Properties

• Melting Point: 117-119 °C
• Boiling Point: 518.414 °C at 760 mmHg
• Flash Point: 185.58 °C
• Appearance: /
• Density: 1.28
• Vapor Pressure: 7.5E-11mmHg at 25°C
• Refractive Index: 1.583
• Storage Temp.: −20°C
• Solubility: Acetone (Slightly), Chloroform (Slightly), DMSO (Slightly, Sonicated), Methanol
• Stability: Moisture Sensitive
• CAS DataBase Reference: 2-Deoxy-alpha-D-erythropentofuranosyl chloride 3,5-bis(4-methylbenzoate)(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Deoxy-alpha-D-erythropentofuranosyl chloride 3,5-bis(4-methylbenzoate)(4330-21-6)
• EPA Substance Registry System: 2-Deoxy-alpha-D-erythropentofuranosyl chloride 3,5-bis(4-methylbenzoate)(4330-21-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 4330-21-6(Hazardous Substances Data)

Usage

Chemical Properties

White solid

Uses

Hoffer''s Chlorosugar is a synthetic precursor for ribose glycosides and ribonucleosides.

InChI:InChI=1/C21H21ClO5/c1-13-3-7-15(8-4-13)20(23)25-12-18-17(11-19(22)26-18)27-21(24)16-9-5-14(2)6-10-16/h3-10,17-19H,11-12H2,1-2H3

Synthetic route

methyl 3,5-di-O-toluoyl-2-deoxy-D-ribofuranose (4330-34-1) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
With acetyl chloride In acetic acid at 20℃;	79%
With hydrogenchloride In acetic acid at 10℃; for 1h;	72%
With hydrogenchloride; acetic acid In 1,4-dioxane	70%

1-O-methyl-2-deoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranose (78185-64-5) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
With hydrogenchloride In diethyl ether at 0℃; for 0.166667h;	72%

D-2-deoxyribose (452-51-7, 13046-70-3, 29780-54-9, 36792-87-7, 36792-88-8, 113890-35-0, 113890-38-3) + 4-methyl-benzoyl chloride (874-60-2) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Stage #1: D-2-deoxyribose With acetyl chloride In methanol at 20℃; for 1.16667h; Inert atmosphere; Stage #2: 4-methyl-benzoyl chloride With pyridine In methanol at 0 - 20℃; Inert atmosphere; Stage #3: With acetic acid; acetyl chloride In methanol at 0℃; Inert atmosphere;	36%

1-O-methyl-2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranose (78185-65-6) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
With hydrogenchloride; acetic acid

D-2-deoxyribose (452-51-7, 13046-70-3, 29780-54-9, 36792-87-7, 36792-88-8, 113890-35-0, 113890-38-3) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: AcCl / 2 h / 20 °C 1.2: DMAP; pyridine / 12 h / 0 °C 2.1: 72 percent / HCl gas / diethyl ether / 0.17 h / 0 °C View Scheme
Multi-step reaction with 3 steps 1: 96 percent / hydrogen chloride / 2 h 2: 85 percent / pyridine / 20 °C 3: 72 percent / HCl / acetic acid / 1 h / 10 °C View Scheme
Multi-step reaction with 3 steps 1: hydrogenchloride / 0.42 h / 20 °C 2: pyridine / 0 - 20 °C / Inert atmosphere 3: hydrogenchloride; acetic acid View Scheme

4-methyl-benzoyl chloride (874-60-2) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: AcCl / 2 h / 20 °C 1.2: DMAP; pyridine / 12 h / 0 °C 2.1: 72 percent / HCl gas / diethyl ether / 0.17 h / 0 °C View Scheme

p-methylbenzoic anhydride (13222-85-0) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 90 percent / NaH / tetrahydrofuran / 4 h / 60 - 70 °C 2: HCl / diethyl ether View Scheme

4-methyl-benzoyl chloride (874-60-2) + resin-bound 4-methylbenzylamine → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / Et3N / acetone 2: HCl / diethyl ether View Scheme
Multi-step reaction with 3 steps 1: Et3N; H2O / acetone / 2 h 2: 90 percent / NaH / tetrahydrofuran / 4 h / 60 - 70 °C 3: HCl / diethyl ether View Scheme

1-O-methyl-2-deoxy-D-ribofuranoside (51255-17-5, 51255-18-6, 60134-26-1, 89577-26-4, 96038-80-1, 96039-31-5, 144301-84-8, 144301-85-9) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / Et3N / acetone 2: HCl / diethyl ether View Scheme
Multi-step reaction with 2 steps 1: 85 percent / pyridine / 20 °C 2: 72 percent / HCl / acetic acid / 1 h / 10 °C View Scheme
Multi-step reaction with 2 steps 1: pyridine / Ambient temperature 2: HCl View Scheme

2-deoxy-D-ribose (22900-10-3, 35536-75-5, 36792-85-5, 113890-34-9, 113890-37-2, 133813-23-7) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: HCl / 0.42 h / Ambient temperature 2: pyridine / Ambient temperature 3: HCl View Scheme

2-deoxy-D-ribose (36792-88-8) → 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: acetyl chloride / 0.5 h / 5 - 10 °C 1.2: 5 h / 5 - 10 °C 2.1: dmap; triethylamine / toluene / 2 h / 25 - 30 °C 3.1: hydrogenchloride; acetyl chloride; acetic acid / 1,4-dioxane; chloroform / 3.25 h / 10 - 15 °C View Scheme

2-chloro-6-(2-pentylimidazol-1-yl)purine (891497-94-2) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-chloro-9-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl]-6-(2-pentylimidazol-1-yl)purine (914084-44-9)

Conditions	Yield
With sodium hydride In dichloromethane; acetonitrile at 0 - 20℃; for 22h;	100%

2-chloro-6-(4,5-diphenylimidazol-1-yl)purine (891497-96-4) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-chloro-9-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl]-6-(4,5-diphenylimidazol-1-yl)purine

Conditions	Yield
With sodium hydride In dichloromethane; acetonitrile at 0 - 20℃; for 22h;	100%
Stage #1: 2-chloro-6-(4,5-diphenylimidazol-1-yl)purine With sodium hydride In acetonitrile at 20℃; for 8h; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In dichloromethane; acetonitrile at 0℃; for 22h;	100%

2-chloro-6-(2-isopropylimidazol-1-yl)purine + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-chloro-9-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl]-6-(2-isopropylimidazol-1-yl)purine

Conditions	Yield
With sodium hydride In dichloromethane; acetonitrile at 0 - 20℃; for 22h;	100%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 5-Cyclohexyl-2,4-bis-trimethylsilanyloxy-pyrimidine (1027429-95-3) → C31H34N2O7 (156899-90-0)

Conditions	Yield
In chloroform Ambient temperature;	99%

2-chloro-6-[2-(2-phenylpropyl)imidazol-1-yl]purine + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-chloro-9-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl]-6-{2-[2-phenylpropyl]imidazol-1-yl}purine

Conditions	Yield
With sodium hydride In dichloromethane; acetonitrile at 0 - 20℃; for 22h;	99%

4,6-difluoro-1H-indole (199526-97-1) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-[2'-deoxy-3',5'-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-4,6-difluoroindole (882043-76-7)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 0.333333h;	99%
With sodium hydride In acetonitrile for 0.333333h;	99%

7-fluoro-1H-indole (387-44-0) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-[2'-deoxy-3',5'-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-7-fluoroindole (943524-12-7)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 0.333333h;	99%
With sodium hydride In acetonitrile for 0.333333h;	99%

3-(2-cyanovinyl)carbazole (1044273-21-3) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → C36H30N2O5 (1044273-22-4)

Conditions	Yield
Stage #1: 3-(2-cyanovinyl)carbazole With potassium hydroxide; Tris(3,6-dioxaheptyl)amine In acetonitrile at 20℃; for 0.5h; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile at 20℃; for 1h;	99%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 5-tert-butyl-2,4-bis-trimethylsilanyloxy-pyrimidine (51223-61-1) → C29H32N2O7 (156899-88-6)

Conditions	Yield
In chloroform Ambient temperature;	98%

4-cyanoindole (16136-52-0) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1'‐(4‐cyano‐1H‐indol‐1‐yl)‐2'‐deoxy‐3',5'‐di‐O‐p‐toluoyl‐β‐D‐ribofuranose

Conditions	Yield
Stage #1: 4-cyanoindole With sodium hydride In acetonitrile; mineral oil at 20℃; for 0.5h; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile; mineral oil at 20℃; for 5.5h;	98%
Stage #1: 4-cyanoindole With sodium hydride In acetonitrile; mineral oil at 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile; mineral oil at 20℃; Inert atmosphere;	72%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 5-Cyclopentyl-2,4-bis-trimethylsilanyloxy-pyrimidine (1026923-77-2) → C30H32N2O7 (156899-89-7)

Conditions	Yield
In chloroform Ambient temperature;	96%

indole (120-72-9) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-(2-deoxy-3,5-di-O-p-toluyl-β-D-ribofuranosyl)indole (118452-10-1)

Conditions	Yield
With sodium hydride In acetonitrile for 0.333333h;	95%
With sodium hydride In acetonitrile at 0℃;	73%
With sodium hydride In acetonitrile at 20℃; for 24h;	54%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + dibutyl 1H-imidazole-4,5-dicarboxylate (59399-27-8) → butyl 1-(2'-deoxy-3',5'-di-O-p-toluoyl-β-D-erythropentofuranosyl)-4,5-imidazoledicarboxylate (620609-09-8)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 3h;	95%

2-chloro-6-(2-propylimidazol-1-yl)purine (891497-90-8) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-chloro-9-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl]-6-(2-propylimidazol-1-yl)purine (914084-41-6)

Conditions	Yield
With sodium hydride In dichloromethane; acetonitrile at 0 - 20℃; for 5h;	95%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 2-trimethylsilylthio-4-trimethylsilyloxypyrimidine (32865-74-0) → 1-(2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-ribofuranosyl)-2-thiouracil (151503-22-9)

Conditions	Yield
With tin(IV) chloride In 1,2-dichloro-ethane at -40℃;	94%
With tin(IV) chloride In various solvent(s) at -40℃; for 6.5h; Mechanism; var. solvents, var. temperat.;	93.9%
With tin(IV) chloride In various solvent(s) at -40℃; for 6.5h;	93.9%

4-fluoroindole (387-43-9) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-[2'-deoxy-3',5'-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-4-fluoroindole (882043-77-8)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 0.333333h;	94%
With sodium hydride In acetonitrile for 0.333333h;	94%

6-fluoro-1H-indole (399-51-9) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-[2'-deoxy-3',5'-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-6-fluoroindole (882043-75-6)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 0.333333h;	94%
With sodium hydride In acetonitrile for 0.333333h;	93%

C19H23N5O2 (1427170-83-9) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → C40H43N5O7 (1427170-93-1) + C40H43N5O7 + C40H43N5O7

Conditions	Yield
Stage #1: C19H23N5O2 With sodium hydride In acetonitrile at 25℃; Inert atmosphere; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile at 25℃; for 2h; Inert atmosphere; regioselective reaction;	A 94% B n/a C n/a

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 5-cyclopropyl-2,4-bis(trimethylsilyloxy)pyrimidine (59968-56-8) → 5-cyclopropyl-1-[2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythropentofuranosyl]uracil (108274-18-6)

Conditions	Yield
In chloroform Ambient temperature;	92%

5-fluoro-1H-indole (399-52-0) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1-[2'-deoxy-3',5'-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-5-fluoroindole (867176-94-1)

Conditions	Yield
With sodium hydride In acetonitrile at 20℃; for 0.333333h;	92%
With sodium hydride In acetonitrile for 0.333333h;	92%
Stage #1: 5-fluoro-1H-indole With sodium hydride In acetonitrile at 20℃; for 0.5h; Metallation; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride for 2h; Substitution;

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 2,5,6-trichloroindole (286949-65-3) → 1-[2-deoxy-3,5-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-2,5,6-trichloroindole (286949-68-6)

Conditions	Yield
Stage #1: 2,5,6-trichloroindole With sodium hydride In acetonitrile at 20℃; for 0.166667h; Metallation; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile for 0.333333h; Glycosylation; Further stages.;	92%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 2-benzylthio-5,6-dichloroindole (286949-64-2) → 2-benzylthio-1-[2-deoxy-3,5-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl]-5,6-dichloroindole (286949-67-5)

Conditions	Yield
Stage #1: 2-benzylthio-5,6-dichloroindole With sodium hydride In acetonitrile at 20℃; for 0.166667h; Metallation; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile for 0.333333h; Glycosylation; Further stages.;	92%

ethynylmagnesium chloride (65032-27-1) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → (2R,3S)-5-ethynyl-2-(((4-methylbenzoyl)oxy)methyl)tetrahydrofuran-3-yl 4-methylbenzoate

Conditions	Yield
In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	92%

5,6-dichlorobenzimidazole (6478-73-5) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 5,6-dichloro-1-(2-deoxy-3,5-di-O-p-toluoyl-β-D-erythro-pentofuranosyl)benzimidazole

Conditions	Yield
Stage #1: 5,6-dichlorobenzimidazole With sodium hydride In acetonitrile at 0 - 20℃; for 1h; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile at 0 - 20℃; for 2h;	92%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 4-chloro-1H-pyrimido[4,5-b]indole (5719-08-4) → 4-chloro-7-(2-deoxy-3,5-di-O-p-toluoyl-β-D-erythro-pentofuranosyl)-7H-pyrimido-[4,5-b]indole (532390-75-3)

Conditions	Yield
Stage #1: 4-chloro-1H-pyrimido[4,5-b]indole With sodium hydride In acetonitrile for 0.166667h; Heating; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile at 20℃; for 1h;	91%

dimethyl 2-bromo-1H-imidazole-4,5-dicarboxylate (705280-65-5) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 2-bromo-1-(2-deoxy-3,5-di-O-p-toluoyl-β-D-erythropentofuranosyl)imidazole-4,5-dicarboxylic acid dimethyl ester (945229-35-6)

Conditions	Yield
With Proton Sponge In acetonitrile at 20℃; for 3h;	91%

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 4,6-dichloro-1H-pyrrolo<3,2-c>pyridine (67139-79-1) → 4,6-Dichloro-1-<2-deoxy-3,5-bis-O-(4-methylbenzoyl)-β-D-erythro-pentofuranosyl>-1H-pyrrolo<3,2-c>pyridine (91713-48-3)

Conditions	Yield
With potassium hydroxide; cryptand TDA-1 In acetonitrile for 0.75h; Ambient temperature;	90%
With sodium hydride 1.) acetonitrile, r.t., 30 min; 2.) 50 deg C, 2 h; Yield given. Multistep reaction;

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → (2R,3S)-5β-azido-2-{[(4-methylbenzoyl)oxy]methyl}tetrahydrofuran-3-yl 4-methylbenzoate (234106-08-2)

Conditions	Yield
With cesium azide In dimethyl sulfoxide	90%
With potassium azide In dimethyl sulfoxide at 20℃; for 1h; Substitution;

2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) + 4-(3-tert-butoxycarbonylamino-propylcarbamoyl)-1H-pyrrole-3-carboxylic acid ethyl ester (439089-47-1) → 4-(3-tert-butoxycarbonylamino-propylcarbamoyl)-1-[4-(4-methyl-benzoyloxy)-5-(4-methyl-benzoyloxymethyl)-tetrahydro-furan-2-yl]-1H-pyrrole-3-carboxylic acid ethyl ester (439089-48-2)

Conditions	Yield
With sodium hydride In acetonitrile	90%

4,5,6,7-tetrafluoro-1H-indole (16264-67-8) + 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride (4330-21-6) → 1',2'-dideoxy-1'-(N-4,5,6,7-tetrafluoroindole)-3',5'-di-O-p-toluoyl-D-ribofuranose

Conditions	Yield
Stage #1: 4,5,6,7-tetrafluoro-1H-indole With sodium hydride In acetonitrile for 0.5h; Stage #2: 2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranosyl chloride In acetonitrile at -5℃; for 1h;	90%

Upstream product

• 78185-64-5 1-O-methyl-2-deoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranose 
• 22900-10-3 2-deoxy-D-ribose 
• 4330-34-1 methyl 3,5-di-O-toluoyl-2-deoxy-D-ribofuranose 
• 452-51-7 D-2-deoxyribose 
• 874-60-2 4-methyl-benzoyl chloride 
• 51255-17-5 1-O-methyl-2-deoxy-D-ribofuranoside 
• 36792-88-8 2-deoxy-D-ribose 
• 13222-85-0 p-methylbenzoic anhydride 
• 78185-65-6 1-O-methyl-2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranose 

Downstream Products

• 50256-07-0 1-[O³,O⁵-bis-(4-methyl-benzoyl)-β-D-erythro-2-deoxy-pentofuranosyl]-6,7-dimethyl-1H-pteridine-2,4-dione 
• 133832-69-6 5-chloro-7-nitro-3-(2-deoxy-3,5-di-O-p-toluoyl-β-D-erythro-pentofuranosyl)-3H-imidazo<4,5-b>pyridine 
• 113574-86-0 1-(2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl)pyrrole-2,4-dicarbonitrile 
• 87008-95-5 3,4-dichloro-1-(3,5-di-O-p-toluoyl-2-deoxy-β-D-erythro-pentofuranosyl)pyridazin-6-one 
• 87008-96-6 3,4-dichloro-1-(3,5-di-O-p-toluoyl-2-deoxy-α-D-erythro-pentofuranosyl)pyridazin-6-one 
• 91713-46-1 6-Chloro-9-(2-deoxy-3,5-di-O-p-toluoyl-β-D-erythro-pentofuranosyl)purine 
• 139244-01-2 6-Chloro-9-(2'-deoxy-3',5'-di-O-p-toluyl-α-D-erythro-pentofuranosyl)purine 
• 73446-74-9 (E)-5-(2-bromovinyl)-2'-deoxy-3',5'-di-O-(p-toluoyl)uridine 
• 73446-75-0 (E)-5-(2-bromovinyl)-1-<2-deoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranosyl>uracil 
• 93366-94-0 2-Amino-7-<2-desoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl>-7H-pyrrolo<2,3-d>pyrimidin 
• 93366-95-1 2-Amino-7-<2-desoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranosyl>-7H-pyrrolo<2,3-d>pyrimidin 
• 96022-80-9 4-Chlor-7-<2-desoxy-3,5-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl>-2-methox-7H-pyrrolo<2,3-d>pyrimidin 
• 96022-81-0 4-Chlor-7-<2-desoxy-3,5-di-O-(p-toluoyl)-α-D-erythro-pentofuranosyl>-2-methoxy-7H-pyrrolo<2,3-d>pyrimidin 
• 100605-54-7 4,6-dichloro-1-<2'-deoxy-3',5'-di-O-(4-toluoyl)-β-D-erythro-pentofuranosyl>-1H-pyrazolo<3,4-d>pyrimidine 

Relevant articles and documents

Benzimidazole derivative BI305 and preparation method and application thereof

The invention discloses a benzimidazole derivative BI305 and a preparation method thereof, and the chemical name of the benzimidazole derivative BI305 is 1-[tetrahydro-4-hydroxy-5-(hydroxymethyl) furan-2-yl]-N, N-dimethyl-1H-benzo [d] imidazole-4-formamide. The benzimidazole derivative and the pharmaceutically acceptable salt, solvate and hydrate thereof have excellent anti-tumor in-vivo and in-vitro activity on MCF-7, SK-BR-3, HCT 116, U-118 MG, U-87 MG and MDA-MB-468, and have a good application prospect in preparation of anti-tumor drugs.

SOLID STATE FORMS OF 5-CHLORO-6-[(2-IMINOPYRROLIDIN-1-YL)METHYL]PYRIMIDINE-2,4-(1H,3H)-DIONE HYDROCHLORIDE AND THEIR PROCESSES FOR THE PREPARATION THEREOF

The present invention relates to solid state forms of 5-chloro-6-[(2-iminopyrrolidin-1-yl)methyl]pyrimidine-2,4-(1H,3H)-dione hydrochloride compound of formula-1a and their processes for the preparation thereof and an improved process for the preparation of 5-chloro-6-[(2-iminopyrrolidin-1-yl)methyl]pyrimidine-2,4-(1H,3H)-dione hydrochloride. The present inventors also provides an amorphous polymorph of the combination drug consisting of 2'-deoxy-5-(trifluoromethyl) uridine and 5-chloro-6-[(2-iminopyrrolidin-1-yl)methyl]pyrimidine-2,4-(1H,3H)-dione monohydrochloride and its process for the preparation.

Preparation of pyridine-stretched 2′-deoxyhypoxanthosine phosphoramidite

Pyridine-stretched 2-deoxyhypoxanthosine (strH) phosphoramidite was prepared in eight steps from Hoffer's sugar (2-deoxy-3,5-di-O-(p-toluoyl)-a-D-erythro-pentofuranosyl chloride). Improved synthesis of the Hoffer sugar was achieved without need for distillation or chromatographic separation of intermediates, or use of gaseous HCl. Conditions were optimised to provide a key nitrile intermediate for the preparation of strH whereby the cesium salt of 4(5)-nitroimidazole was glycosylated using Hoffer's sugar. The nitrile intermediate was also used to prepare pyridine-stretched 2-deoxyadenosine (strA) and pyridine-stretched 2-deoxy-2,6-diaminonebulamine (strD). Preliminary studies indicate that strH forms a stronger, size-expanded base pair with adenine compared with the Watson-Crick thymine-adenine base pair.