85-31-4

Basic information

• Product Name: 6-THIOGUANOSINE
• Synonyms: 2-AMINO-6-MERCAPTOPURINE RIBOSIDE;6-MERCAPTOGUANOSINE;6-MERCAPTO-2-AMINOPURINE RIBOSIDE;6-THIOGUANOSINE;2-amino-1,9-dihydro-9-beta-d-ribofuranosyl-6h-purine-6-thion;2-amino-6-mercapto-9(beta-d-ribofuranosyl)purine;2-amino-6-mercaptopurineribonucleoside;2-amino-9-(beta-d-ribofuranosyl)purine-6-thiol
• CAS NO: 85-31-4
• Molecular Formula: C₁₀H₁₃N₅O₄S
• Molecular Weight: 299.31
• EINECS: 201-597-2
• Product Categories: Nucleotides and Nucleosides;Bases & Related Reagents;Nucleotides;Sulfur & Selenium Compounds
• Mol File: 85-31-4.mol
• Article Data: 3

Chemical Properties

• Melting Point: 230-231°C
• Boiling Point: 756.9 °C at 760 mmHg
• Flash Point: 411.6 °C
• Appearance: Yellow-Green Powder
• Density: 2.18
• Vapor Pressure: 3.44E-24mmHg at 25°C
• Refractive Index: 1.6460 (estimate)
• Storage Temp.: -20°C Freezer
• PKA: 13.21±0.70(Predicted)
• CAS DataBase Reference: 6-THIOGUANOSINE(CAS DataBase Reference)
• NIST Chemistry Reference: 6-THIOGUANOSINE(85-31-4)
• EPA Substance Registry System: 6-THIOGUANOSINE(85-31-4)

Safety Data

• Safety Statements: 24/25
• RTECS: UP0200000
• Hazardous Substances Data: 85-31-4(Hazardous Substances Data)

Usage

Chemical Properties

Tan Powder

Uses

antineoplastic

Purification Methods

Thioguanosine is crystallised (as hemihydrate) from hot H2O (charcoal) and cooled slowly to give tapered prisms. It also crystallises by dissolving in dilute NH3 and acidifying with acetic acid, and then recrystallising from H2O. UV: (pH 4-6) max at 257nm ( 8,820) and 342nm ( 24,800), and (pH 10.4-12.0) max at 252nm ( 14,700) and 319.5nm ( 21,000). [Fox et al. J Am Chem Soc 80 1667 1958, Beilstein 26 III/IV 3927.]

InChI:InChI=1/C10H13N5O4S/c11-10-13-7-4(8(20)14-10)12-2-15(7)9-6(18)5(17)3(1-16)19-9/h2-3,5-6,9,16-18H,1H2,(H3,11,13,14,20)/p-1/t3-,5-,6-,9-/m1/s1

Synthetic route

O2',O3',O5'-tribenzoyl-6-thio-guanosine (88010-92-8) → 6-thioguanosine (85-31-4)

Conditions	Yield
With sodium ethanolate

G (118-00-3) → 6-thioguanosine (85-31-4)

Conditions	Yield
With pyridine; sodium hydrogensulfide; trifluoroacetic anhydride 1) 40 min, ice-bath, 2) DMF, 24 h; Multistep reaction;

2',3',5'-tri-O-benzoylguanosine (66048-53-1) → 6-thioguanosine (85-31-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: aqueous pyridine; P2S5 2: ethanolic sodium ethylate View Scheme

2,4-Dinitrofluorobenzene (70-34-8) + 6-thioguanosine (85-31-4) → (2R,3R,4S,5R)-2-[2-Amino-6-(2,4-dinitro-phenylsulfanyl)-purin-9-yl]-5-hydroxymethyl-tetrahydro-furan-3,4-diol (74418-21-6)

Conditions	Yield
With triethylamine	80%
With triethylamine

6-thioguanosine (85-31-4) → 6-amino-1-β-D-ribofuranosylimidazo<4,5-c>pyridine-4-sulfenamide (123002-38-0)

Conditions	Yield
With potassium hydroxide; chloroamine for 0.75h; from 0 deg C to RT;	74%
With potassium hydroxide; chloroamine at 0℃; for 1.5h;	73.7%

triethylamine carbonate (15715-58-9) + 6-thioguanosine (85-31-4) → 6-thioguanosine 5'-O-monophosphate triethylammonium salt

Conditions	Yield
Stage #1: 6-thioguanosine With trimethyl phosphite; trichlorophosphate at 0℃; for 48h; Stage #2: triethylamine carbonate In water	68%

cobalt(II) nitrate hexahydrate + 6-thioguanosine (85-31-4) → [Co(6-thioGuo)3] sesquihydrate

Conditions	Yield
In methanol; water at 86℃; for 3h;	48%

cobalt(II) sulphate heptahydrate + 6-thioguanosine (85-31-4) → [bis(6-thioguanosine-k2N,S)(6-thioguanosinato-k2N,S)cobalt(III)] sulphate trihydrate

Conditions	Yield
With sodium hydroxide In water for 3h; pH=8; Reflux;	15%

6-thioguanosine (85-31-4) → thioguanine (154-42-7) + α-D-ribofuranosyl-1-phosphate (18646-11-2)

Conditions	Yield
With E. coli purine nucleoside phosphorylase Enzyme kinetics; Substitution;

6-thioguanosine (85-31-4) → N2-phenoxyacetyl-S6-(2,4-dinitrophenyl)-6-thioguanosine (623164-06-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 80 percent / triethylamine 2: NH3 / H2O View Scheme
Multi-step reaction with 4 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 View Scheme

6-thioguanosine (85-31-4) → 9-((2R,3R,4R,5R)-3,4-Bis-trimethylsilanyloxy-5-trimethylsilanyloxymethyl-tetrahydro-furan-2-yl)-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-ylamine

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / triethylamine View Scheme
Multi-step reaction with 2 steps 1: Et3N 2: pyridine View Scheme

6-thioguanosine (85-31-4) → N-[9-(3,4-bis-trimethylsilanyloxy-5-trimethylsilanyloxymethyl-tetrahydro-furan-2-yl)-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-yl]-2-phenoxy-acetamide

Conditions	Yield
Multi-step reaction with 3 steps 1: 80 percent / triethylamine View Scheme
Multi-step reaction with 3 steps 1: Et3N 2: pyridine 3: pyridine View Scheme

6-thioguanosine (85-31-4) → N-[9-{3,4-dihydroxy-5-[(4-methoxy-phenyl)-diphenyl-methoxymethyl]-tetrahydro-furan-2-yl}-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-yl]-2-phenoxy-acetamide (623164-07-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: 80 percent / triethylamine 2: NH3 / H2O 3: pyridine View Scheme
Multi-step reaction with 5 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 5: pyridine View Scheme

6-thioguanosine (85-31-4) → N-[9-{3-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-5-[(4-methoxy-phenyl)-diphenyl-methoxymethyl]-tetrahydro-furan-2-yl}-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-yl]-2-phenoxy-acetamide (623164-08-9)

Conditions	Yield
Multi-step reaction with 6 steps 1: 80 percent / triethylamine 2: NH3 / H2O 3: pyridine 4: pyridine; AgNO3 View Scheme
Multi-step reaction with 6 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 5: pyridine 6: AgNO3; pyridine View Scheme

6-thioguanosine (85-31-4) → Diisopropyl-phosphoramidous acid (2R,3R,4R,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-[6-(2,4-dinitro-phenylsulfanyl)-2-(2-phenoxy-acetylamino)-purin-9-yl]-2-[(4-methoxy-phenyl)-diphenyl-methoxymethyl]-tetrahydro-furan-3-yl ester 2-cyano-ethyl ester

Conditions	Yield
Multi-step reaction with 7 steps 1: 80 percent / triethylamine 2: NH3 / H2O 3: pyridine 4: pyridine; AgNO3 5: N,N-di(isopropyl)ethylamine View Scheme
Multi-step reaction with 7 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 5: pyridine 6: AgNO3; pyridine 7: i-Pr2NEt / 12 h / 10 °C View Scheme

6-thioguanosine (85-31-4) → N-[9-{4-(tert-butyl-dimethyl-silanyloxy)-3-hydroxy-5-[(4-methoxy-phenyl)-diphenyl-methoxymethyl]-tetrahydro-furan-2-yl}-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-yl]-2-phenoxy-acetamide

Conditions	Yield
Multi-step reaction with 6 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 5: pyridine 6: AgNO3; pyridine View Scheme

6-thioguanosine (85-31-4) → N-[9-{3,4-bis-(tert-butyl-dimethyl-silanyloxy)-5-[(4-methoxy-phenyl)-diphenyl-methoxymethyl]-tetrahydro-furan-2-yl}-6-(2,4-dinitro-phenylsulfanyl)-9H-purin-2-yl]-2-phenoxy-acetamide

Conditions	Yield
Multi-step reaction with 6 steps 1: Et3N 2: pyridine 3: pyridine 4: aq. NH3 5: pyridine 6: AgNO3; pyridine View Scheme

6-thioguanosine (85-31-4) → 2-amino-9-β-D-ribofuranosylpurine-6-sulfonamide (123002-39-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 74 percent / chloramine, 2 N KOH / 0.75 h / from 0 deg C to RT 2: 86.7 percent / m-chloroperoxybenzoic acid (MCPBA) / aq. ethanol / 18 h / Ambient temperature View Scheme

6-thioguanosine (85-31-4) → (RS)-2-amino-9-β-D-ribofuranosylpurine-6-sulfinamide (124508-99-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 73.7 percent / ClNH2, 2 N KOH / 1.5 h / 0 °C 2: 67 percent / 85percent 3-chloroperoxybenzoic acid / ethanol / 0.25 h / 0 - 5 °C View Scheme

6-thioguanosine (85-31-4) → (R)-2-amino-9-β-D-ribofuranosylpurine-6-sulfinamide (123002-46-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 74 percent / chloramine, 2 N KOH / 0.75 h / from 0 deg C to RT 2: 1.) m-chloroperoxybenzoic acid (MCPBA) / ethanol; H2O / 19 h / Ambient temperature View Scheme

6-thioguanosine (85-31-4) → (S)-2-amino-9-β-D-ribofuranosylpurine-6-sulfinamide (123002-47-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 74 percent / chloramine, 2 N KOH / 0.75 h / from 0 deg C to RT 2: 1.) m-chloroperoxybenzoic acid (MCPBA) / ethanol; H2O / 19 h / Ambient temperature View Scheme

6-thioguanosine (85-31-4) → C10H12Cl2N5O5PS

Conditions	Yield
Stage #1: 6-thioguanosine With trimethyl phosphite; lutidine at 0℃; for 0.166667h; Stage #2: With trichlorophosphate for 1h;
With trimethyl phosphite; trichlorophosphate

bis(cyclopentadienyl)titanium dichloride (1271-19-8) + 6-thioguanosine (85-31-4) → Ti(C5H5)2(6-thioguanineribose) dichloride complex

Conditions	Yield
In methanol under N2 either in glove box or in double-manifold vac.; 1 equiv. of 6-thioguanineribose; mixted at room temp.; mixt. stirred for 8-12 h; solid isolated in fritted funnel of fine porosity; dried in vac. at 45°C for 12 h; elem. anal.;

bis(cyclopentadienyl)molybdenum(IV) dichloride (12184-22-4) + 6-thioguanosine (85-31-4) → [(η5-cyclopentadienyl)2Mo((-)-2-amino-6-mercaptopurine riboside)]Cl2

Conditions	Yield
In tetrahydrofuran; methanol stirring at room temp. for 8 h; ppt. was filtered off, washed with cold THF, dried in vac., recrystd. from cold MeOH, dried in vac. for 12 h at 30°C; elem. anal.;

6-thioguanosine (85-31-4) → C22H32N10O17P3S(1+)*3C6H15N

Conditions	Yield
Multi-step reaction with 3 steps 1: trimethyl phosphite; trichlorophosphate / 48 h / 0 °C 2: 2,2'-dipyridyldisulphide; triethylamine; triphenylphosphine / N,N-dimethyl-formamide 3: zinc(II) chloride / N,N-dimethyl-formamide View Scheme

6-thioguanosine (85-31-4) → 6-thioguanosine 5'-O-phosphorimidazolide lithium salt (1616389-41-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: trimethyl phosphite; trichlorophosphate / 48 h / 0 °C 2: 2,2'-dipyridyldisulphide; triethylamine; triphenylphosphine / N,N-dimethyl-formamide View Scheme

6-thioguanosine (85-31-4) → C22H32N10O16P3S2(1+)*3C6H15N

Conditions	Yield
Multi-step reaction with 3 steps 1: trimethyl phosphite; trichlorophosphate / 48 h / 0 °C 2: 2,2'-dipyridyldisulphide; triethylamine; triphenylphosphine / N,N-dimethyl-formamide 3: zinc(II) chloride / N,N-dimethyl-formamide View Scheme

6-thioguanosine (85-31-4) → C22H29N10O17P3S(2-)*3Na(1+)

Conditions	Yield
Multi-step reaction with 4 steps 1: trimethyl phosphite; trichlorophosphate / 48 h / 0 °C 2: 2,2'-dipyridyldisulphide; triethylamine; triphenylphosphine / N,N-dimethyl-formamide 3: zinc(II) chloride / N,N-dimethyl-formamide 4: sodium perchlorate / water; acetone View Scheme

Upstream product

• 154985-75-8 6-thioguanine 
• 58-96-8 uridine 
• 66048-53-1 2',3',5'-tri-O-benzoylguanosine 
• 118-00-3 G 
• 88010-92-8 O^2'_,O3'_,O5'-tribenzoyl-6-thio-guanosine 

Downstream Products

• 154-42-7 thioguanine 
• 18646-11-2 α-D-ribofuranosyl-1-phosphate 
• 124508-99-2 3-deazasulfinosine 
• 123002-39-1 2-amino-9-β-D-ribofuranosylpurine-6-sulfonamide 
• 129944-21-4 N²-benzoyl-9-{5'-O-(4,4'-dimethoxytriphenylmethyl)-2'-O-[(tert-butyl)dimethylsilyl]-β-D-ribofuranosyl}-9H-purin-2-amine 3'-(2-cyanoethyl N,N-diisopropylphosphoramidite) 
• 129944-20-3 N²-benzoyl-9-{5'-O-(4,4'-dimethoxytriphenylmethyl)-2'-O-[(tert-butyl)dimethylsilyl]-β-D-ribofuranosyl}-9H-purin-2-amine 
• 129944-19-0 N-benzoyl-9-[5'-O-(4,4'-dimethoxytriphenylmethyl)-β-D-ribofuranosyl]-9H-purin-2-amine 
• 129944-18-9 N-benzoyl-9-(β-D-ribofuranosyl)-9H-purin-2-amine 
• 74418-21-6 (2R,3R,4S,5R)-2-[2-Amino-6-(2,4-dinitro-phenylsulfanyl)-purin-9-yl]-5-hydroxymethyl-tetrahydro-furan-3,4-diol 
• 4914-73-2 (2R,3R,4S,5R)-2-[2-amino-6-(methylthio)-9H-purin-9-yl]-5-(hydroxymethyl)tetrahydrofuran-3,4-diol 
• 4546-54-7 2?amino?9?(β?D?ribofuranosyl)purine 
• 88010-97-3 4-[2-Amino-9-((2R,3R,4S,5R)-3,4-dihydroxy-5-hydroxymethyl-tetrahydro-furan-2-yl)-9H-purin-6-ylsulfanyl]-1-(4-fluoro-phenyl)-butan-1-one 
• 123002-38-0 2-amino-9-β-D-ribofuranosylpurine-6-sulfenamide 

Relevant articles and documents

Aeromonas hydrophila strains as biocatalysts for transglycosylation

Microbial transglycosylation is useful as a green alternative in the preparation of purine nucleosides and analogues, especially for those that display pharmacological activities. In a search for new transglycosylation biocatalysts, two Aeromonas hydrophila strains were selected. The substrate specificity of both micro-organisms was studied and, as a result, several nucleoside analogues have been prepared. Among them, ribavirin, a broad spectrum antiviral, and the well-known anti HIV didanosine, were prepared, in 77 and 62% yield using A. hydrophila CECT 4226 and A. hydrophila CECT 4221, respectively. In order to scale-up the processes, the reaction conditions, product purification and biocatalyst preparation were analyzed and optimized.

One-flask syntheses of 6-thioguanosine and 27′-deoxy-6-thioguanosine

We have previously reported that reaction of guanosine or 2′-deoxyguanosine with trifluoroacetic anhydride in pyridine gives a putative 6-pyridyl intermediate from which several 6-substituted derivatives may be obtained.1 We now report high-yield conversion of guanosine and 2′deoxyguanosine to the corresponding 6-thio compounds in a two-step, one-flask reaction via this 6-pyridyl intermediate. Standard Raney nickel treatment, as reported for the ribonucleoside,2 then gives the 2-aminopurine nucleosides.