5872-08-2

Basic information

• Product Name: DL-10-CAMPHORSULFONIC ACID
• Synonyms: DL-10-CAMPHORSULPHONIC ACID;DL-10-CAMPHORSULFONIC ACID;DL-10-CAMPHORSULFONIC ACID N-HYDRATE;D-(+)-10-CAMPHORSULFONIC ACID MONOHYDRATE;(+/-)-CAMPHOR-10-SULPHONIC ACID;(+/-)-CAMPHOR-10-SULFONIC ACID (BETA);(+/-)-CAMPHOR-10-SULFONIC ACID;CAMPHOR-10-SULFONIC ACID
• CAS NO: 5872-08-2
• Molecular Formula: C₁₀H₁₆O₄S
• Molecular Weight: 232.3
• EINECS: 227-527-0
• Product Categories: Pharmaceutical Intermediates;FINE Chemical & INTERMEDIATES;Bicyclic Monoterpenes;Biochemistry;Reagents for Oligosaccharide Synthesis;Terpenes;Organic AcidsOrganic Conductors and Photovoltaics: OFET and OPV Materials;Chemical Synthesis;Conducting Polymers and Monomers;Polyanilines and Polyaniline Dopants;Synthetic Reagents
• Mol File: 5872-08-2.mol
• Article Data: 5

Chemical Properties

• Melting Point: 203-206 °C (dec.)(lit.)
• Boiling Point: 344.46°C (rough estimate)
• Appearance: Slightly beige/Granular Powder
• Density: 1.2981 (rough estimate)
• Refractive Index: 1.5400 (estimate)
• Storage Temp.: 2-8°C
• PKA: 1.17±0.50(Predicted)
• Water Solubility: Soluble in water.
• Sensitive: Hygroscopic
• Stability: Stable. Incompatible with strong bases, strong oxidizing agents. Combustible.
• BRN: 3205973
• CAS DataBase Reference: DL-10-CAMPHORSULFONIC ACID(CAS DataBase Reference)
• NIST Chemistry Reference: DL-10-CAMPHORSULFONIC ACID(5872-08-2)
• EPA Substance Registry System: DL-10-CAMPHORSULFONIC ACID(5872-08-2)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45-27
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 3
• RTECS: DT5077100
• F: 3-10
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 5872-08-2(Hazardous Substances Data)

Usage

Overview

DL-Camphorsulfonic acid, also known as camphorsulfonic acid, is a white or almost white crystalline powder. The molecular formula of camphorsulfonic acid is C10H16O4S. It is a pair of chiral optical enantiomers with prismatic crystals, divided into left-handed camphorsulfonic acid and right-handed camphorsulfonic acid. The melting point is 193~195 ℃ and 197~200 ℃, respectively. Camphorsulfonic acid is a derivative of camphor, widely used in medicine, light industry and cosmetic industry. At present, its application mainly focused on chiral asymmetric synthesis, high selective catalysis of natural products and polymer doping with polyaniline to prepare nano-scale conductive polymer materials. Figure 1: left-right isomer of camphorsulfonic acid

Preparation

natural camphor is mainly extracted from camphor plants, ginger plants and sage seeds, and with optical activity; synthetic camphor is generally prepared by the isomerization of turpentine to obtain camphene, then by esterification, hydrolysis and dehydrogenation reaction process; synthetic camphor is racemic, almost lacking optical activity. Through the reaction of camphor powder and concentrated sulfuric acid sulfonation, racemic camphorsulfonic acid is obtained, and then by the resolution, left and right handed camphorsulfonic acid is made. The optimum conditions for the synthesis of camphorsulfonic acid are as follows: the molar ratio of camphor powder, concentrated sulfuric acid and acetic anhydride is 1.0: 1.4: 3.0; reaction temperature is10 ℃; standing time is 5 days, and camphorsulfonic acid is vacuum dried. Utilizing sopropyl alcohol as solvent, camphor sulfonate is obtained by neutralization of camphorsulfonic acid and a resolving agent made by alcohol amine; camphorsulfonic acid is obtained by purification. Figure 2: Preparation principle

Resolution

Kinetic resolution is the selective chiral reduction of racemic camphor, so that one of the enantiomers of racemates is selectively reducted, leaving the required isomers, and then purifying. It is also possible to add optically active amino acids, phenylglycine, phenylalanine, hydroxyphenylglycine, o-chlorophenylglycine and resolving agents of its derivatives. Subjecting racemic camphorsulfonic acid to salting treatment, separating the left and right camphorsulfonic acid ammonium salt solution by chromatography, film evaporation, crystallization and filtration; drying to get white crystals, the left and right handed camphorsulfonic acid is made.

Uses

Different sources of media describe the Uses of 5872-08-2 differently. You can refer to the following data:
1. Pharmaceutical intermediates, optical split agent. Camphorsulfonic acid is an important organic synthesis intermediates, optical resolving agent. Due to its optical rotation, it is industrially applicable be the optical isomers for racemisation, and is also widely used as pharmaceutical intermediates such as for the production of intestinal disorder inhibitors, HIV improving agents and the like. Left and right handed camphorsulfonic acid is an important resolving agent for optically active amino acids, such as camphorsulfonic acid—a chiral ion-pairing reagent. It separates 5 substances—phenylpropanolamine, which has receptor-blocking action and cardiac inhibition and local anesthetic action effects; metoprolol, propranolol, epinephrine, salbutamol and atenolol. Camphor sulfonate made by camphorsulfonic acid for salting or other synthetic routes also has a wide range of uses. For example, camphor sulfonate is a veterinary central stimulant, which can stimulate the respiratory center and cause respiratory excitement, ; it is used for the treatment respiratory and circulatory acute disorders, resisting central nervous system poisoning; camphor ammonium sulfonate acts as a chiral ion pair reagent added to the mobile phase to separate the aromatic alcohol amine drug enantiomers. Figure 3: Camphor sulfonate
2. (+)-Camphor-10-sulfonic acid is used as a resolving agent for chiral amines and other cations. It is involved in the preparation of active pharmaceutical ingredient such as trimetaphan camsilate, which is used to reduce bleeding during neurosurgery. Further, it is involved in the transglucosidation of methyl and ethyl D-glucopyranosides by alcoholysis.

Market

The domestic demand for camphorsulfonic acid is high; camphorsulfonic acid is basically dependent on imports, and the price of it is also very expensive, especially for L-camphorsulfonic acid.

References

[1] KE Chunlan, LIU Xiaohong, XU Chunxiao etc. Synthesis and Resolution of Camphor Sulfonic Acid [J]. Journal of Nanchang University Engineering, 2010, 32 (4): 381-384. [2] KE Chunlan, LIU Xiaohong, XU Chunxiao etc. Synthesis and latest application of chiral camphorsulfonic acid and its salts [J] .Jiangxi Chemical Industry, 2010 (2): 1-4.

Chemical Properties

DL-10-CAMPHORSULFONIC ACID is white to off-white powder

General Description

Camphorsulfonic acid is a organosulphur compound.

InChI:InChI=1/C10H16O4S/c1-9(2)7-3-4-10(9,8(11)5-7)6-15(12,13)14/h7H,3-6H2,1-2H3,(H,12,13,14)

Synthetic route

Camphor (76-22-2) → 10-camphorsufonic acid (5872-08-2)

Conditions	Yield
With sulfuric acid; acetic anhydride

(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (464-49-3) → 10-camphorsufonic acid (5872-08-2)

Conditions	Yield
With sulfuric acid; acetic anhydride Reychler method;

dl-camphor → 10-camphorsufonic acid (5872-08-2)

Conditions	Yield
With sulfuric acid; acetic anhydride

10-camphorsufonic acid (5872-08-2) + bis-[(trifluoroacetoxy)iodo]benzene (2712-78-9) → [di((camphorsulfonyl)oxy)iodo]benzene

Conditions	Yield
In acetonitrile at 20℃; for 3h; Inert atmosphere;	98%

10-camphorsufonic acid (5872-08-2) → (2,2,3-Trimethyl-cyclopent-3-enyl)-acetic acid (25435-53-4)

Conditions	Yield
With potassium hydroxide at 200 - 220℃; for 0.0833333h; Retro-Prins fragmentation;	90%

Trimethyl orthoacetate (1445-45-0) + 10-camphorsufonic acid (5872-08-2) → (+/-)-2-oxo-bornane-10-sulfonic acid methyl ester (46471-67-4, 62319-13-5, 83603-04-7)

Conditions	Yield
In dichloromethane at 20℃;	89%
In dichloromethane at 20℃;	89%

10-camphorsufonic acid (5872-08-2) + alfuzosin (81403-80-7) → N1-(4-amino-6,7-dimethoxyquinazol-2-yl)-N1-methyl-N2-(tetrahydrofuro-2-yl)propylenediamine (7,7-dimethyl-2-oxo-bicyclo[2,2,1]hept-1-yl)methanesulfonate

Conditions	Yield
In ethyl acetate at 20 - 50℃; Product distribution / selectivity; Inert atmosphere;	88%

2-(tetrahydro-2H-pyran-2-yl)-N-(3-(9-(tetrahydro-2H-pyran-2-yl)-9H-purin-6-yl)pyridin-2-yl)-2H-indazol-4-amine (1253568-74-9) + 10-camphorsufonic acid (5872-08-2) → N-(3-(9H-purin-6-yl)pyridin-2-yl)-1H-indazol-4-amine (+/-)-10-camphorsulfonate

Conditions	Yield
In methanol; dichloromethane at 40℃; for 22h;	86%

10-camphorsufonic acid (5872-08-2) → ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl chloride (6994-93-0)

Conditions	Yield
With thionyl chloride In N,N-dimethyl-formamide at 0 - 20℃; for 4.5h;	85%
With trichloroacetonitrile; triphenylphosphine In dichloromethane for 1h; Heating;

10-camphorsufonic acid (5872-08-2) + alfuzosin hydrochloride (81403-68-1) → N1-(4-amino-6,7-dimethoxyquinazol-2-yl)-N1-methyl-N2-(tetrahydrofuro-2-yl)propylenediamine (7,7-dimethyl-2-oxo-bicyclo[2,2,1]hept-1-yl)methanesulfonate

Conditions	Yield
Stage #1: alfuzosin hydrochloride With sodium hydroxide In dichloromethane; water Stage #2: 10-camphorsufonic acid In dichloromethane at 20 - 40℃; Product distribution / selectivity;	84%

10-camphorsufonic acid (5872-08-2) + 1,3,3-Trimethyl-5-nitro-2-{(E)-3-[1,3,3-trimethyl-5-nitro-1,3-dihydro-indol-(2E)-ylidene]-propenyl}-2,3-dihydro-1H-indol-2-ol → 1,3,3,1',3',3'-Hexamethyl-5,5'-dinitroindocarbocyanine dl-10-camphorsulfonate

Conditions	Yield
With potassium hydroxide In methanol; water	81%

9-methyl-3-oxa-9-azatricyclo[3.3.1.0(2,4)]non-7-yl hydroxy(di-2-thienyl)acetate + 10-camphorsufonic acid (5872-08-2) → C10H15O4S(1-)*C19H22NO4S2(1+)

Conditions	Yield
In dichloromethane; acetonitrile at 20℃; for 24h;	80%

brucine (357-57-3) + 10-camphorsufonic acid (5872-08-2) → (1S)-10-camphorsulfonic acid (3144-16-9) + (R)-10-camphorsulfonic acid (35963-20-3)

10-camphorsufonic acid (5872-08-2) → (1S)-10-camphorsulfonic acid (3144-16-9)

Conditions	Yield
With brucine man zerlegt das ausscheideten Brucinsalz der -β-sulfonsaeure mit Barytwasser;
With brucine

10-camphorsufonic acid (5872-08-2) → (R)-10-camphorsulfonic acid (35963-20-3)

Conditions	Yield
With hydrogenchloride; d-phenylglycine
With brucine

10-camphorsufonic acid (5872-08-2) → Potassium; ((1S,4R)-7,7-dimethyl-2-oxo-bicyclo[2.2.1]hept-1-yl)-methanesulfonate (21791-95-7)

Conditions	Yield
With potassium hydroxide

10-camphorsufonic acid (5872-08-2) → C10H15PS4

Conditions	Yield
With tetraphosphorus decasulfide; tetra(n-butyl)ammonium hydroxide 2.) toluene, reflux, 16h; Yield given. Multistep reaction;

hydrogenchloride (7647-01-0) + (S)-2-phenylglycine (2935-35-5) + 10-camphorsufonic acid (5872-08-2) → (1S)-10-camphorsulfonic acid (3144-16-9) + (R)-10-camphorsulfonic acid (35963-20-3)

10-camphorsufonic acid (5872-08-2) → N-phenethyl-10-camphorsulfonamide

Conditions	Yield
Multi-step reaction with 2 steps 1: Cl3CCN; PPh3 / CH2Cl2 / 1 h / Heating 2: 4-picoline / CH2Cl2 / 1 h / 20 °C View Scheme

10-camphorsufonic acid (5872-08-2) → (+/-)-6-(camphor-10-sulfonamido)-hexanoic acid

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 85 percent / SOCl2 / dimethylformamide / 4.5 h / 0 - 20 °C 2.1: MgO / H2O; dioxane / 0.25 h / Heating 2.2: 65 percent / H2O; dioxane / 16 h View Scheme

10-camphorsufonic acid (5872-08-2) → (+/-)-6-(camphorquinone-10-sulfonamido)-hexanoic acid

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 85 percent / SOCl2 / dimethylformamide / 4.5 h / 0 - 20 °C 2.1: MgO / H2O; dioxane / 0.25 h / Heating 2.2: 65 percent / H2O; dioxane / 16 h 3.1: SeO2 / H2O; dioxane / 120 h / Heating View Scheme

10-camphorsufonic acid (5872-08-2) → 10 bromocamphor (1925-54-8, 64161-50-8, 116783-25-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: KOH 2: PBr3 3: xylene / Heating; Dallacker et al. method View Scheme

10-camphorsufonic acid (5872-08-2) → (+)-10-bromo-2-chloro-2-nitrosocamphane

Conditions	Yield
Multi-step reaction with 5 steps 1: KOH 2: PBr3 3: xylene / Heating; Dallacker et al. method 4: NH2OH-HCl 5: Cl2 gas / diethyl ether / 0 °C / Davidson method View Scheme

10-camphorsufonic acid (5872-08-2) → 10-bromocamphor oxime

Conditions	Yield
Multi-step reaction with 4 steps 1: KOH 2: PBr3 3: xylene / Heating; Dallacker et al. method 4: NH2OH-HCl View Scheme

10-camphorsufonic acid (5872-08-2) → ((1S,4R)-7,7-Dimethyl-2-oxo-bicyclo[2.2.1]hept-1-yl)-methanesulfonyl bromide

Conditions	Yield
Multi-step reaction with 2 steps 1: KOH 2: PBr3 View Scheme

Ph(3-Cl)(5-OCHF2)-(R)CH(OH)C(O)-Aze-Pab(OMe) (433937-93-0) + 10-camphorsufonic acid (5872-08-2) → C10H16O4S*C22H23ClF2N4O5

4,4'-diformylbiphenyl (66-98-8) + 10-camphorsufonic acid (5872-08-2) → C34H36O8S2(2-)*2Na(1+)

Conditions	Yield
Stage #1: 10-camphorsufonic acid With sodium methylate In methanol; toluene at 25 - 66℃; Stage #2: 4,4'-diformylbiphenyl In methanol; toluene at 66 - 70℃; for 7h;

2-methylspiro(1,3-oxathiolane-5,3'-quinuclidine) (124620-88-8) + 10-camphorsufonic acid (5872-08-2) → cis-2-methylspiro(1,3-oxathiolane-5,3')quinuclidine camphorsulfonic acid salt

Conditions	Yield
In methanol; toluene at 20℃; for 22h;	12.04 g

10-camphorsufonic acid (5872-08-2) → (1S)-10-camphorsulfonic acid (3144-16-9) + (R)-10-camphorsulfonic acid (35963-20-3)

Conditions	Yield
With barium(II) perchlorate In methanol Solvent; Reagent/catalyst; Resolution of racemate;

Upstream product

• 464-49-3 (1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one 
• 76-22-2 Camphor 
• 736109-58-3 1,7,7-trimethyl-bicyclo[2.2.1]heptan-2-one 

Downstream Products

• 10413-17-9 6-phenyltetrahydropyran-2-one 
• 676165-94-9 N-[benzo[1,3]dioxol-5-yl-(toluene-4-sulfonyl)-methyl]-formamide 
• 141631-85-8 3-(2',5'-dimethoxybenzylidene)camphor-10-sulfonic acid 
• 111040-56-3 1-benzyl-2-(2,2-dimethoxy)propyl-3-octadecylglycerol 
• 186664-64-2 cis-6-(Ethoxy)-3a,8a-di-(hydro)-3H-8-oxacyclopenta[a]indene-5-ol 
• 909279-85-2 clopidogrel camphorsulfonate 
• 1234389-39-9 tetrabutylphosphonium salicylate-camphorsulfonic acid 
• 1280142-53-1 [Ag((+/-)-camphor-10-sulfonato)(4-aminobenzoic acid)](n) 

Relevant articles and documents

Identification of small molecule sulfonic acids as ecto-5'-nucleotidase inhibitors

Ecto-5'-Nucleotidase inhibitors have great potential as anti-tumor agents. We have investigated biochemical properties of human and rat ecto-5'-Nucleotidases and characterized 19 small molecule sulfonic acid derivatives as potential inhibitors of ecto-5'-Nucleotidases. We identified 11 potent inhibitors of human and rat ecto-5'-Nucleotidases and checked their selectivity. Compound 10 (Sodium 2,4-dinitrobenzenesulfonate) with Ki value of 0.66 μM and 19 (N-(4- sulfamoylphenylcarbamothioyl) pivalamide) with Ki value of 0.78 μM were identified as the most potent inhibitors for human and rat ecto-5'-Nucleotidase, respectively. The present compounds have low molecular weights, water solubility and equal potency as compared to the reported inhibitors.

Dibenzonaphthyrones

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Process for the preparation of D(-)αphenylglycine

The invention provides a process for the preparation of D(-)αphenylglycine by resolution of DLαphenylglycine by means of D(+)camphorsulfonic acid. The present process enables the preparation of D(-)αphenylglycine at a minimum loss of the very expensive starting materials, such as DLαphenylglycine and D(+)camphorsulfonic acid. The salts produced in this process are precipitated from the resolution filtrate and the filtrate may be discarded as effluent water without any danger to the environment.