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METHYL 5-ACETYLSALICYLATE, also known as methyl ester of acetylsalicylic acid, is a white to light yellow-orange crystalline powder with a variety of applications in different industries. It is a derivative of salicylic acid and possesses both anti-inflammatory and analgesic properties.

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  • 16475-90-4 Structure
  • Basic information

    1. Product Name: METHYL 5-ACETYLSALICYLATE
    2. Synonyms: Methyl 5-acetylsalicylate, 98.0%(GC);enzoic acid,5-acetyl-2-hydroxy-, methyl ester;Benzoic acid, 5-acetyl-2-hydroxy-, methyl ester;5-ACETYLSALICYLIC ACID METHYL ESTER;5-ACETYL-2-HYDROXYBENZOIC ACID METHYL ESTER;5-ACETYL 2-METHYLSALICYLATE;METHYL 2-HYDROXY-5-ACETYLBENZOATE;METHYL 5-ACETYLSALICYLATE
    3. CAS NO:16475-90-4
    4. Molecular Formula: C10H10O4
    5. Molecular Weight: 194.18
    6. EINECS: 240-532-2
    7. Product Categories: Aromatic Esters;Esters;Phenyls & Phenyl-Het;Phenyls & Phenyl-Het;C10 to C11;Carbonyl Compounds;Aromatics;Miscellaneous Reagents
    8. Mol File: 16475-90-4.mol
  • Chemical Properties

    1. Melting Point: 62-64 °C(lit.)
    2. Boiling Point: 167 °C / 15mmHg
    3. Flash Point: 138 °C
    4. Appearance: white to light yellow-orange crystalline powder
    5. Density: 1.0583 (rough estimate)
    6. Vapor Pressure: 3.1E-05mmHg at 25°C
    7. Refractive Index: 1.5168 (estimate)
    8. Storage Temp.: Refrigerator
    9. Solubility: Soluble in methanol.
    10. PKA: 7.96±0.18(Predicted)
    11. BRN: 2643824
    12. CAS DataBase Reference: METHYL 5-ACETYLSALICYLATE(CAS DataBase Reference)
    13. NIST Chemistry Reference: METHYL 5-ACETYLSALICYLATE(16475-90-4)
    14. EPA Substance Registry System: METHYL 5-ACETYLSALICYLATE(16475-90-4)
  • Safety Data

    1. Hazard Codes: Xi
    2. Statements: 36/37/38
    3. Safety Statements: 26-36
    4. WGK Germany: 3
    5. RTECS:
    6. HazardClass: N/A
    7. PackingGroup: N/A
    8. Hazardous Substances Data: 16475-90-4(Hazardous Substances Data)

16475-90-4 Usage

Uses

Used in Food Industry:
METHYL 5-ACETYLSALICYLATE is used as a flavoring agent and preservative in the food industry. Its unique properties contribute to enhancing the taste and extending the shelf life of various food products.
Used in Pharmaceutical Industry:
METHYL 5-ACETYLSALICYLATE is used as an analgesic and anti-inflammatory agent for the relief of headache and muscle and joint aches. Its effectiveness in reducing fever, inflammation, and swelling makes it a valuable component in the treatment of rheumatoid arthritis, rheumatic fever, and mild infections.
Used in Cosmetics Industry:
Although not explicitly mentioned in the provided materials, METHYL 5-ACETYLSALICYLATE could potentially be used in the cosmetics industry for its anti-inflammatory and analgesic properties, particularly in products aimed at soothing and reducing skin inflammation or irritation.

Preparation

Obtained by heating a solution of 5-acetyl-2-hydroxybenzoic acid and sulfuric acid in methanol for 24 h (82%).

Check Digit Verification of cas no

The CAS Registry Mumber 16475-90-4 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 1,6,4,7 and 5 respectively; the second part has 2 digits, 9 and 0 respectively.
Calculate Digit Verification of CAS Registry Number 16475-90:
(7*1)+(6*6)+(5*4)+(4*7)+(3*5)+(2*9)+(1*0)=124
124 % 10 = 4
So 16475-90-4 is a valid CAS Registry Number.
InChI:InChI=1/C10H10O4/c1-6(11)7-3-4-9(12)8(5-7)10(13)14-2/h3-5,12H,1-2H3

16475-90-4 Well-known Company Product Price

  • Brand
  • (Code)Product description
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  • Alfa Aesar

  • (A10215)  Methyl 5-acetylsalicylate, 98%   

  • 16475-90-4

  • 25g

  • 685.0CNY

  • Detail
  • Alfa Aesar

  • (A10215)  Methyl 5-acetylsalicylate, 98%   

  • 16475-90-4

  • 100g

  • 2653.0CNY

  • Detail

16475-90-4SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 10, 2017

Revision Date: Aug 10, 2017

1.Identification

1.1 GHS Product identifier

Product name METHYL 5-ACETYLSALICYLATE

1.2 Other means of identification

Product number -
Other names 5-Acetylsalicylic Acid Methyl Ester

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:16475-90-4 SDS

16475-90-4Synthetic route

methanol
67-56-1

methanol

5-acetylsalicylic acid
13110-96-8

5-acetylsalicylic acid

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With sulfuric acid for 24h; Heating;96%
With thionyl chloride at 65℃; for 24h; Inert atmosphere;
2-acetoxy-5-acetyl-benzoic acid methyl ester

2-acetoxy-5-acetyl-benzoic acid methyl ester

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With ytterbium(III) triflate In isopropyl alcohol for 20h; Deacetylation; Heating;95%
acetic anhydride
108-24-7

acetic anhydride

methyl salicylate
119-36-8

methyl salicylate

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With aluminium trichloride In dichloromethane for 3h; Friedel-Crafts reaction;93%
With aluminum (III) chloride In dichloromethane at -5 - 10℃; for 20h; Inert atmosphere;83.3%
With aluminum (III) chloride In nitrobenzene at 120 - 180℃; for 0.133333h; Temperature; Time; Pressure; Friedel-Crafts Acylation; Microwave irradiation;100 %Chromat.
5-acetyl-2-(3-methyl-but-2-enyloxy)-benzoic acid methyl ester

5-acetyl-2-(3-methyl-but-2-enyloxy)-benzoic acid methyl ester

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With ytterbium(III) triflate In nitromethane for 1h; Ambient temperature;74%
3-acetyl-3',3'-dicyano-5-methoxycarbonylxanthyrone
72554-64-4

3-acetyl-3',3'-dicyano-5-methoxycarbonylxanthyrone

A

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

B

4-Hydroxyacetophenone
99-93-4

4-Hydroxyacetophenone

Conditions
ConditionsYield
With water for 3h; Product distribution; Heating; other xanthyrones;A 41%
B 16%
3-acetyl-3'-cyano-3',5-bismethoxycarbonylxanthyrone
72554-63-3

3-acetyl-3'-cyano-3',5-bismethoxycarbonylxanthyrone

A

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

B

4-Hydroxyacetophenone
99-93-4

4-Hydroxyacetophenone

Conditions
ConditionsYield
With water for 3h; Product distribution; Heating; other xanthyrones;A 41%
B 16%
acetic acid
64-19-7

acetic acid

methyl salicylate
119-36-8

methyl salicylate

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With PPA at 80℃; for 2h;20%
methyl acetylsalicylate
580-02-9

methyl acetylsalicylate

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With aluminium trichloride; nitrobenzene
2-methoxybenzoic acid methyl ester
606-45-1

2-methoxybenzoic acid methyl ester

acetyl chloride
75-36-5

acetyl chloride

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With carbon disulfide; aluminium trichloride
3'-acetyl-3,5,5'-trismethoxycarbonylglaucyrone
74823-33-9, 78075-03-3

3'-acetyl-3,5,5'-trismethoxycarbonylglaucyrone

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With water for 3h; Product distribution; Heating; other glaucyrones;
acetyl chloride
75-36-5

acetyl chloride

methyl salicylate
119-36-8

methyl salicylate

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With aluminium trichloride In 1,1,2,2-tetrachloroethylene
In 1,1,2,2-tetrachloroethylene
3-carbomethoxy-4-hydroxy-α-bromoacetophenone
36256-45-8

3-carbomethoxy-4-hydroxy-α-bromoacetophenone

A

2-Hydroxy-5-((R)-1-hydroxy-ethyl)-benzoic acid methyl ester

2-Hydroxy-5-((R)-1-hydroxy-ethyl)-benzoic acid methyl ester

B

methyl 5-(2-bromo-1-hydroxyethyl)-2-hydroxybenzoate

methyl 5-(2-bromo-1-hydroxyethyl)-2-hydroxybenzoate

C

(R)-methyl 5-(2-bromo-1-hydroxyethyl)-2-hydroxybenzoate

(R)-methyl 5-(2-bromo-1-hydroxyethyl)-2-hydroxybenzoate

D

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
With sodium formate; cetyltrimethylammonim bromide; sodium dodecyl-sulfate; (R,R)-TsDPEN; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In water at 28℃; for 5h; Title compound not separated from byproducts;
aspirin
50-78-2

aspirin

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
Multi-step reaction with 2 steps
1: 82 percent / AlCl3 / nitrobenzene / 1 h
2: 96 percent / H2SO4 / 24 h / Heating
View Scheme
1,1,2,2-tetrachloroethylene
127-18-4

1,1,2,2-tetrachloroethylene

acetyl chloride
75-36-5

acetyl chloride

methyl salicylate
119-36-8

methyl salicylate

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

Conditions
ConditionsYield
aluminium chloride40 g (43%)
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

benzyl bromide
100-39-0

benzyl bromide

5-acetyl-2-benzyloxybenzoic acid methyl ester
27475-09-8

5-acetyl-2-benzyloxybenzoic acid methyl ester

Conditions
ConditionsYield
With potassium carbonate In acetonitrile at 85℃; for 9h;100%
With potassium carbonate In acetonitrile at 75℃; for 16h;100%
With potassium carbonate In acetonitrile for 24h;96.6%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

ethylene glycol
107-21-1

ethylene glycol

2-[4-hydroxy-3-(methoxycarbonyl)phenyl]-2-methyl-1,3-dioxolane
467429-12-5

2-[4-hydroxy-3-(methoxycarbonyl)phenyl]-2-methyl-1,3-dioxolane

Conditions
ConditionsYield
With Triisopropoxymethan; cerium triflate In hexane at 25℃; for 2h;99%
With toluene-4-sulfonic acid In toluene for 16h; Heating;91%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

1-(4'-hydroxy-3'-methoxycarbonylphenyl)ethanol
66654-06-6

1-(4'-hydroxy-3'-methoxycarbonylphenyl)ethanol

Conditions
ConditionsYield
With CdS(x)Se(1-x) x:0-1;; cesium acetate; para-thiocresol In toluene for 10h; Sealed tube; Inert atmosphere; Irradiation;99%
With sodium tetrahydroborate; boric acid for 1.5h;60 % Chromat.
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

benzyl chloride
100-44-7

benzyl chloride

5-acetyl-2-benzyloxybenzoic acid methyl ester
27475-09-8

5-acetyl-2-benzyloxybenzoic acid methyl ester

Conditions
ConditionsYield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 50 - 65℃; for 2h;98.5%
With sodium carbonate In N,N-dimethyl-formamide at 110 - 115℃; for 2h;84.7%
With sodium In ethanol for 30h; Heating;55%
With sodium carbonate; sodium iodide In acetonitrile for 16h; Heating / reflux;55%
With potassium carbonate
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

trimethyleneglycol
504-63-2

trimethyleneglycol

2-[4-hydroxy-3-(methoxycarbonyl)phenyl]-2-methyl-1,3-dioxane
1171247-80-5

2-[4-hydroxy-3-(methoxycarbonyl)phenyl]-2-methyl-1,3-dioxane

Conditions
ConditionsYield
With Triisopropoxymethan; cerium triflate In hexane at 25℃; for 2h;98%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

heptyl halide

heptyl halide

methyl 5-acetyl-2-heptyloxybenzoate
1373427-92-9

methyl 5-acetyl-2-heptyloxybenzoate

Conditions
ConditionsYield
Stage #1: estere metilico dell'acido 5-acetilsalicilico With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: heptyl halide In N,N-dimethyl-formamide at 50℃; for 5h;
97.6%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

methyl halide

methyl halide

5-acetyl-2-methoxybenzoic acid methyl ester
39971-36-3

5-acetyl-2-methoxybenzoic acid methyl ester

Conditions
ConditionsYield
Stage #1: estere metilico dell'acido 5-acetilsalicilico With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: methyl halide In N,N-dimethyl-formamide at 50℃; for 5h;
97%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

methyl iodide
74-88-4

methyl iodide

5-acetyl-2-methoxybenzoic acid methyl ester
39971-36-3

5-acetyl-2-methoxybenzoic acid methyl ester

Conditions
ConditionsYield
With sodium carbonate In N,N-dimethyl-formamide96.5%
With sodium carbonate In DMF (N,N-dimethyl-formamide) at 0 - 20℃; for 3h;96.5%
With sodium carbonate In DMF (N,N-dimethyl-formamide) at 0 - 20℃; for 3h;96.5%
trifluoromethylsulfonic anhydride
358-23-6

trifluoromethylsulfonic anhydride

estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

5-acetyl-2-(trifluoro-methyl-sulfonyloxy)-benzoic acid,methyl ester
343338-97-6

5-acetyl-2-(trifluoro-methyl-sulfonyloxy)-benzoic acid,methyl ester

Conditions
ConditionsYield
With pyridine In dichloromethane at 0℃; for 0.5h;96%
With pyridine In dichloromethane at 0℃; for 0.833333h;96%
With triethylamine at -40℃;
With 2,6-dimethylpyridine; dmap In dichloromethane at -30 - 20℃; for 3h;
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

hexyl halide

hexyl halide

methyl 5-acetyl-2-hexyloxybenzoate
1373427-91-8

methyl 5-acetyl-2-hexyloxybenzoate

Conditions
ConditionsYield
Stage #1: estere metilico dell'acido 5-acetilsalicilico With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: hexyl halide In N,N-dimethyl-formamide at 50℃; for 5h;
95.9%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

octyl halide

octyl halide

methyl 5-acetyl-2-octyloxybenzoate
1373427-93-0

methyl 5-acetyl-2-octyloxybenzoate

Conditions
ConditionsYield
Stage #1: estere metilico dell'acido 5-acetilsalicilico With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: octyl halide In N,N-dimethyl-formamide at 50℃; for 5h;
93.5%
estere metilico dell'acido 5-acetilsalicilico
16475-90-4

estere metilico dell'acido 5-acetilsalicilico

butyl halide

butyl halide

methyl 5-acetyl-2-butoxybenzoate

methyl 5-acetyl-2-butoxybenzoate

Conditions
ConditionsYield
Stage #1: estere metilico dell'acido 5-acetilsalicilico With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 20℃; for 1h;
Stage #2: butyl halide In N,N-dimethyl-formamide at 50℃; for 5h;
92%

16475-90-4Relevant articles and documents

Energy efficiency in chemical reactions: A comparative study of different reaction techniques

Gronnow, Mark J.,White, Robin J.,Clark, James H.,Macquarrie, Duncan J.

, p. 516 - 518 (2005)

Metrics for chemists are much argued, but the energy usage of a reaction has to be one of the most simple and effective methods of comparing technologies. In this concept paper, the energy consumed in preparing one mole of a chemical compound is compared for a variety of technologies. Data are gathered for traditional oil bath, supercritical CO2 (sc-CO 2), and microwave reactors. Two different Suzuki couplings, a Knoevenagel condensation, and a Friedel-Crafts acylation are all compared in both the microwave and oil bath, as this is where the most noticeable differences were observed. The most notable result was an 85-fold reduction in energy demand on switching from oil bath to microwave reactor for a Suzuki reaction.

Preparation method of free racemic albuterol

-

Paragraph 0039; 0040, (2018/12/13)

The invention discloses a preparation method of free racemic albuterol. The preparation method comprises the following steps: with methyl salicylate as a raw material, successively carrying out Friedel-Crafts acylation and oxidation, carrying out condensation and borate reduction in pure water with a 'one-pot' method, carrying out ester group reduction and acetonylidene protection of crude albuterol with a 'one-pot' method, and carrying out deprotection and purification to obtain the free racemic albuterol. The preparation method has the advantages of high labor efficiency, low reaction reagent cost and high yield.

Enantioselective bromolactonization of conjugated (2)-enynes

Zhang, Wei,Zheng, Suqing,Liu, Na,Werness, Jenny B.,Guzei, Llia A.,Tang, Weiplng

supporting information; experimental part, p. 3664 - 3665 (2010/05/15)

"Chemical equation presented" A catalytic enantioselective syn-1,4-bromolactonization of conjugated (Z)-enynes was reported. Diastereomeric ratios >20:1 and up to 99% enantiomeric excesses were observed. Di-, tri-, and tetra-substituted bromoallenes were prepared together with lactone heterocycles efficiently and stereoselectively. Preliminary investigations suggest that the chiral catalyst may serve as a bifunctional reagent by interacting with both a carboxylic acid nucleophile and NBS electrophile.

Asymmetric transfer hydrogenation of ketones catalyzed by hydrophobic metal-amido complexes in aqueous micelles and vesicles

Wang, Fei,Liu, Hui,Cun, Linfeng,Zhu, Jin,Deng, Jingen,Jiang, Yaozhong

, p. 9424 - 9429 (2007/10/03)

Asymmetric transfer hydrogenation of ketones, especially α-bromomethyl aromatic ketones, catalyzed by unmodified, hydrophobic transition metal-amido complexes (TsDPEN-M), was performed successfully with significant enhancement of activity, chemoselectivity, and enantio-selectivity (up to 99% ee) in aqueous media containing micelles and vesicles. The hydrophobic catalyst, embedded in micelles constructed from the surfactant cetyltrimethylammonium bromide (CTAB), could be separated from the organic phase along with the products and was recycled for at least six times.

Mass tags for quantitative analysis

-

, (2008/06/13)

The present invention relates generally to novel protein modification reagents for fractionation and quantitative (differential) profiling of proteins in a complex mixture. The reagents react with amino acids or other protein components or structures and function as mass tags. The present invention provides methods of making the protein modification reagents and methods of using the protein modification reagents for quantitative analysis of proteins.

Dual binding mode of methylmethanetriacetic acid to tripodal amidopyridine receptors

Ballester, Pablo,Capo, Magdalena,Costa, Antoni,Deya, Pere M.,Gomila, Rosa,Decken, Andreas,Deslongchamps, Ghislain

, p. 8832 - 8841 (2007/10/03)

A series of tripodal amidopyridine receptors capable of selective recognition of methylmethanetriacetic acid (MMTA) in organic solvents is described. Intramolecular hydrogen-bonding groups, built into some of the receptors, were designed as preorganization devices. Binding was studied by NMR titration, variable temperature NMR experiments, 2D-NMR, isothermal titration calorimetry, and single-crystal X-ray crystallography. The results reveal that a balancing act between inter- and intramolecular hydrogen-bonding interactions in the complexes governs both the dynamics and the geometry of binding. Receptor 1b (without intramolecular hydrogen-bonding groups) features a simple symmetric MMTA binding geometry with optimal enthalpic interactions. In sharp contrast, receptor 1a (with intramolecular hydrogen-bonding groups) reveals a temperature-dependent dual binding mode where MMTA can bind in two completely different geometries. The two solution binding geometries of 1a·MMTA were unraveled by NMR experiments and correlated to the X-ray structures.

Alternative routes to pterulone

Kahnberg, Pia,Lee, Choon Woo,Grubbs, Robert H,Sterner, Olov

, p. 5203 - 5208 (2007/10/03)

Two new synthetic routes to pterulone, a fungal metabolite possessing potent antifungal activity as an inhibitor of NADH/ubiquinone oxidoreductase, are reported.

Ytterbium triflate mediated selective deprotection of acetates

Sharma,Ilangovan

, p. 1963 - 1965 (2007/10/03)

Ytterbium triflate mediated selective deprotection of acetates in isopropyl alcohol at reflux temperature is reported. Unlike hafnium triflate, under the present reaction conditions aryl acetates also undergo deacetylation instead of Fries migration.

Polyketoenols and Chelates. New Types of Xanthyrones Lacking Enolised Side-chain Termini: their Reactions with Magnesium Methoxide

Baker, S. Richard,Crombie Leslie,Dove, Roderick V.

, p. 165 - 171 (2007/10/02)

Xanthyrones (4) and (8) as well as (9), (11) and (13) have been synthesised: blocking the side-chain terminus, which is normally enolised as in (5), by dicyano or cyano-ester end groups, leads to enolisation of the 3-acetylpyrone end as shown by n.m.r. data in CDCl3.The dicyanobismethoxycarbonyl representative (9) exists in the 1'-H form in CDCl3-CF3CO2H whilst in CDCl3 the tetraester (13) is a 3'-H form.Xanthyrone (11) is present mainly in the 3'-H form in CDCl3 but some enolate (12) is observed.All the xanthyrones are highly ionised in ethanol, (9) especially so.Treated with exess (>6 mol. equiv.) magnesium methoxide, xanthyrones (4) and (8) cyclise by an aldol pathway and (9) and (13) by an analogous Claisen pathway.This contrasts with dimethylxanthophanic enol (5) with undergoes a different type of Claisen cyclisation.The results accord with the view that cyclisation in the latter case involves a bischelate (20) and in the other cases monochelates, e.g. (22) and (25).Reactions of xanthyrones (4) and (8) with boiling water follow expected pathways.

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