14667-55-1

Basic information

• Product Name: Trimethyl-pyrazine
• Synonyms: TRIMETHYLPYRAZINE;TRIMETHYLPYRAZINE,2,3,5;FEMA 3244;FEMA NUMBER 3244;2,3,6-TRIMETHYLPYRAZINE;2,3,5-TRIMETHYLPYRAZINE;trimethyl-pyrazin;2 3 5-TRIMETHYLPYRAZINE 99+% FCC
• CAS NO: 14667-55-1
• Molecular Formula: C₇H₁₀N₂
• Molecular Weight: 122.17
• EINECS: 238-712-0
• Product Categories: Pyrazines;Heterocyclic Compounds;Mono- & Polyalkylpyrazines;pyrazine Flavor;Building Blocks;Heterocyclic Building Blocks;Alphabetical Listings;Flavors and Fragrances;Q-Z;Pyrazine compounds;Building Blocks;Chemical Synthesis;Heterocyclic Building Blocks
• Mol File: 14667-55-1.mol

Chemical Properties

• Melting Point: 156 °C
• Boiling Point: 171-172 °C(lit.)
• Flash Point: 130 °F
• Appearance: clear yellow liquid
• Density: 0.979 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.72mmHg at 25°C
• Refractive Index: n20/D 1.5040(lit.)
• Storage Temp.: Flammables area
• PKA: 2.69±0.10(Predicted)
• BRN: 2423
• CAS DataBase Reference: Trimethyl-pyrazine(CAS DataBase Reference)
• NIST Chemistry Reference: Trimethyl-pyrazine(14667-55-1)
• EPA Substance Registry System: Trimethyl-pyrazine(14667-55-1)

Safety Data

• Hazard Codes: Xn
• Statements: 10-22-36/37/38
• Safety Statements: 16-26-36/37/39
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• RTECS: UQ3907000
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 14667-55-1(Hazardous Substances Data)

Usage

Chemical Properties

Different sources of media describe the Chemical Properties of 14667-55-1 differently. You can refer to the following data:
1. CLEAR YELLOW LIQUID
2. 2,3,5-Trimethylpyrazine has a baked potato or roasted nut aroma.

Occurrence

Reported present in bakery products, roasted barley, cocoa products, coffee, dairy products, meat, peanuts, filberts, pecans, popcorn, potato products, rum and whiskey, soy products, raw asparagus, baked potato, wheaten bread, crispbread, Swiss cheese, coffee, black tea, green tea, roasted barley, roasted filbert, heated beef, roasted peanut, soybean, raw beans, coriander seed, scallop, guava, kohlrabi, bell pepper, blue, Swiss and Gruyere cheese, boiled egg, fatty fish, beer, sherry, barley, peanut, oat products, coconut, beans, mushroom, trassi, almond, macadamia nut, sesame seed, coriander seed, rice, licorice, sweet corn, malt, peated malt, wort, krill, fermented shrimp, crab, okra, crayfish, clam, scallop and squid.

Uses

Different sources of media describe the Uses of 14667-55-1 differently. You can refer to the following data:
1. Trimethylpyrazine is a key aroma compound of dark chocolates differing in organoleptic properties.
2. 2,3,5-Trimethylpyrazine can be used as a flavor ingredient in food industries.

Preparation

From 2,5-dimethylpyrazine by ring alkylation with MeLi; by condensing propylenediamine with 2,3-butanedione.

Aroma threshold values

Detection: 400 ppb to 9 ppm (9 ppm in water)

Taste threshold values

Taste characteristics at 80 ppm: raw, musty, nutty and potato.

General Description

2,3,5-Trimethylpyrazine is present in brown cheese.

Safety Profile

Moderately toxic by ingestion. Combustible liquid. When heated to decomposition emits toxic fumes of NOx.

InChI:InChI=1/C7H10N2/c1-5-4-8-6(2)7(3)9-5/h4H,1-3H3

Synthetic route

2,5-dimethyl-3-chloropyrazine (95-89-6) + trimethylaluminum (75-24-1) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; hexane for 2h; Heating;	64%

2,3-dimethyl-5-trifluoromethanesulfonyloxypyrazine (1147535-04-3) + zinc methyl bromide (18815-74-2) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran at 20℃; for 12h; Negishi coupling reaction; Inert atmosphere;	61%

2,3-dimethyl-5-trifluoromethanesulfonyloxypyrazine (1147535-04-3) + dimethyl zinc(II) (544-97-8) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran at 20℃; for 12h; Inert atmosphere;	38%

2,5-dimethyl-pyrazine (123-32-0) + methyllithium (917-54-4) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With diethyl ether

N-methyl-2,5-dimethylpyrazinium bromide (88234-17-7) → Tetramethylpyrazine (1124-11-4) + 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
at 275 - 280℃;

2,3,5-trimethylpiperazine (89940-71-6) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With aluminum oxide; copper oxide-chromium oxide silicon dioxide aluminium oxide catalyst; water; silica gel at 375℃;

C9H14N2O3 (133129-02-9, 133129-06-3, 149470-70-2) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
In toluene at 300℃; Yield given;

D-(+)-Glucose (54-17-1, 492-61-5, 492-62-6, 492-66-0, 530-25-6, 530-26-7, 530-27-8, 530-28-9, 552-76-1, 579-36-2, 643-69-6, 655-45-8, 2280-44-6, 3646-73-9, 7282-78-2, 7282-79-3, 7282-80-6, 7282-81-7, 7282-82-8, 7283-02-5, 7283-08-1, 7283-09-2, 7283-10-5, 7283-11-6, 7296-15-3, 7296-64-2, 7322-31-8, 10257-28-0, 12772-65-5, 12773-29-4, 12773-31-8, 12773-32-9, 12773-33-0, 12773-34-1, 19982-85-5, 28538-24-1, 32445-46-8, 32445-47-9, 32445-51-5, 32445-52-6, 34685-56-8, 34685-57-9, 35810-56-1, 39281-65-7, 39281-66-8, 39281-67-9, 39281-68-0, 39281-69-1, 39392-61-5, 39392-62-6, 39392-63-7, 39392-65-9, 39392-66-0, 39392-69-3, 40825-84-1, 40825-86-3, 40825-87-4, 40825-89-6, 42752-07-8, 42789-83-3, 46032-76-2, 54808-89-8, 66069-07-6, 120442-57-1, 120442-58-2, 120442-59-3, 120442-67-3, 131064-91-0, 131064-92-1, 131065-00-4, 131065-01-5, 131348-38-4) → 1,4-pyrazine (290-37-9) + 2-Methylpyrazine (109-08-0) + 2,5-dimethyl-pyrazine (123-32-0) + 2,3-dimethylpyrazine (5910-89-4) + 2,6-dimethylpyrazine (108-50-9) + 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
With ammonium hydroxide In glycerol for 9h; Product distribution; Heating; also with amino acids;

3-amino-2-propanol (78-96-6, 1674-56-2) → 1,4-pyrazine (290-37-9) + 2-Methylpyrazine (109-08-0) + 2,5-dimethyl-pyrazine (123-32-0) + 2-ethyl-3,6-dimethylpyrazine (13360-65-1) + 2,3,5-trimethylpyrazine (14667-55-1) + 1-aminoethyl-2-methylaziridine

Conditions	Yield
With copper chromite at 180℃; for 0.333333h; Product distribution; var. temp.; other aminoalcohols;

DL-methionine (59-51-8) → 1,4-pyrazine (290-37-9) + 2-Methylpyrazine (109-08-0) + 2,5-dimethyl-pyrazine (123-32-0) + methyl 3-(methylthio)propionate (13532-18-8) + 2,3,5-trimethylpyrazine (14667-55-1) + 1-<3-(methylthio)propyl>-2-formylpyrrole

Conditions	Yield
With alpha-D-glucopyranose In water at 180℃; for 1h; Product distribution; also with methionine sulfoxide and without glucose;

2.5-dimethyl-pyrazine-mono bromomethylate → Tetramethylpyrazine (1124-11-4) + 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
at 270 - 280℃;

D-Glucose (2280-44-6) + L-leucine (61-90-5) → 1,4-pyrazine (290-37-9) + 2-Methylpyrazine (109-08-0) + 2,5-dimethyl-pyrazine (123-32-0) + 2,3-dimethylpyrazine (5910-89-4) + 2,6-dimethylpyrazine (108-50-9) + 2,3,5-trimethylpyrazine (14667-55-1) + var. alkyl substituted pyrazines

Conditions	Yield
With ammonium hydroxide In glycerol at 120℃; for 4h; Product distribution; var. times, solvents, temp., and ratios of reactants, also without leucine;

...Expand

3-[(Z)-Allylimino]-butan-2-one oxime (133128-90-2) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium tert-butoxide / dimethylsulfoxide / 2 h / 50 °C 2: Et3N / CH2Cl2 / 10 - 20 °C 3: toluene / 300 °C View Scheme

3-{(E)-[(Z)-Propenyl]imino}-butan-2-one oxime (133128-94-6, 133128-98-0, 149470-69-9) → 2,3,5-trimethylpyrazine (14667-55-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: Et3N / CH2Cl2 / 10 - 20 °C 2: toluene / 300 °C View Scheme

Upstream product

• 123-32-0 2,5-dimethyl-pyrazine 
• 917-54-4 methyllithium 
• 88234-17-7 N-methyl-2,5-dimethylpyrazinium bromide 
• 89940-71-6 2,3,5-trimethylpiperazine 
• 95-89-6 2,5-dimethyl-3-chloropyrazine 
• 75-24-1 trimethylaluminum 
• 133129-02-9 C₉H₁₄N₂O₃ 
• 78-96-6 3-amino-2-propanol 
• 59-51-8 DL-methionine 
• 2280-44-6 D-Glucose 
• 61-90-5 L-leucine 
• 133128-90-2 3-[(Z)-Allylimino]-butan-2-one oxime 
• 133128-94-6 3-{(E)-[(Z)-Propenyl]imino}-butan-2-one oxime 
• 50-99-7 D-glucose 

Downstream Products

• 86461-68-9 1-(2,3,5-Trimethyl-6-pyrazinyl)-1-propanone 
• 13515-06-5 5,6-Dimethylpyrazin-2-carbonsaeure 
• 89940-71-6 2,3,5-trimethylpiperazine 
• 95407-83-3 1,3,7-Trimethyl-pyrrolo[1,2-a]pyrazine 
• 95407-84-4 1,3,6,7-Tetramethyl-pyrrolo[1,2-a]pyrazine 
• 95407-85-5 1,3-Dimethyl-7-phenyl-pyrrolo[1,2-a]pyrazine 
• 921040-00-8 2-chloromethyl-3,6-dimethylpyrazine 
• 921040-02-0 (Chloromethyl)dimethylpyrazine 
• 921040-01-9 5,6-dimethyl-2-chloromethylpyrazine 
• 46187-37-5 2-Isobutyl-3,5,6-trimethylpyrazin 
• 1400563-39-4 (3,5-dimethylpyrazin-2-yl)methanol 
• 1400563-40-7 (3,6-dimethylpyrazin-2-yl)methanol 
• 68303-35-5 2-chloro-3,5,6-trimethylpyrazine 

Relevant articles and documents

Comparison of pyrazines formation in methionine/glucose and corresponding Amadori rearrangement product model

The generation of pyrazines in a binary methionine/glucose (Met/Glc) mixture and corresponding methionine/glucose-derived Amadori rearrangement product (MG-ARP) was studied. Quantitative analyses of pyrazines and methional revealed that MG-ARP generated more methional compared to Met/Glc, whereas lower content and fewer species of pyrazines were observed in the MG-ARP model. Comparing the availability of α-dicarbonyl compounds generated from the Met/Glc model, methylglyoxal (MGO) was a considerably effective α-dicarbonyl compound for the formation of pyrazines during MG-ARP degradation, but glyoxal (GO) produced from MG-ARP did not effectively participate in the corresponding formation of pyrazines due to the asynchrony on the formation of GO and recovered Met. Diacetyl (DA) content was not high enough to form corresponding pyrazines in the MG-ARP model. The insufficient interaction of precursors and rapid drops in pH limited the formation of pyrazines during MG-ARP degradation. Increasing reaction temperature could reduce the negative inhibitory effect by promoting the content of precursors.

Synthesis and pyrolysis of two flavor precursors of oct-1-en-3-yl methylpyrazinecarboxylates

To rich flavor additive species of pyrazines, two new compounds of 3,6-dimethyl-2,5-pyrazinedicarboxylic acid 1-octen-3-yl ester (DMPOE) and 3,5,6-trimethyl-2-pyrazinecarboxylic acid 1-octen-3-yl ester (TMPOE) were synthesized by KMnO4 oxidatio

1H-pyrrole-2,4-dicarbonyl-derivatives and their use as flavoring agents

The present invention primarily relates to 1H-pyrrole-2,4-dicarbonyl-derivatives of Formula (I) wherein R1, R2, R3, Z. Z' and J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) or of a mixture of compounds of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.

Imidazo[1,2-a]pyridine-ylmethyl-derivatives and their use as flavoring agents

The present invention primarily relates to imidazo[1,2-a]pyridine-ylmethyl-derivatives of Formula (I) wherein R1, R2, X, W e J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.

Regioselective synthesis of trialkylpyrazines via nickel-catalyzed Negishi cross-coupling of pyrazine triflate

A regioselective synthesis of trialkylpyrazines via nickel-catalyzed cross-coupling reaction of pyrazine triflate is reported. The 5-substituted 2,3-dimethylpyrazine derivatives including trail pheromone components of the ant Eutetramorium mocquerysi have been successfully synthesized in good yields by nickel-catalyzed Negishi cross-coupling reactions of pyrazine triflate mediated by alkyl and arylzinc halides. Georg Thieme Verlag Stuttgart · New York.

Formation of pyrazines in maillard model systems of lysine-containing dipeptides

Whereas most studies concerning the Maillard reaction have focused on free amino acids, little information is available on the impact of peptides and proteins on this important reaction in food chemistry. Therefore, the formation of flavor compounds from the model reactions of glucose, methylglyoxal, or glyoxal with eight dipeptides with lysine at the N-terminus was studied in comparison with the corresponding free amino acids by means of stir bar sorptive extraction (SBSE) followed by GC-MS analysis. The reaction mixtures of the dipeptides containing glucose, methylglyoxal, and glyoxal produced 27, 18, and 2 different pyrazines, respectively. Generally, the pyrazines were produced more in the case of dipeptides as compared to free amino acids. For reactions with glucose and methylglyoxal, this difference was mainly caused by the large amounts of 2,5(6)-dimethylpyrazine and trimethylpyrazine produced from the reactions with dipeptides. For reactions with glyoxal, the difference in pyrazine production was rather small and mostly unsubstituted pyrazine was formed. A reaction mechanism for pyrazine formation from dipeptides was proposed and evaluated. This study clearly illustrates the capability of peptides to produce flavor compounds that can differ from those obtained from the corresponding reactions with free amino acids.

Volatile Compounds Generated from Thermal Reaction of Methionine and Methionine Sulfoxide with or without Glucose

Methionine and methionine sulfoxide were mixed with or without glucose in distilled water, individually.These solutions were heated in closed sample cylinders at 180 deg C for 1 h.The volatile compounds generated were extracted using methylene chloride and analyzed by GC and GC-MS.Pyrazine compounds, especially 2,5-dimethyl-, 2-ethyl-5-methyl-, trimethyl-, and methylpyrazines were the predominant compounds among those generated from thermal interactions of glucose and methionine or methionine sulfoxide.The formation of methional or those compounds derived for methional was found to be more favorable from the thermal degradation of methionine, whereas the formation of dimethyl polysulfides, especially dimethyl disulfide and dimethyl trisulfide, was found to be more favorable from the thermal degradation of methionine sulfoxide.Glucose was found to have a catalytic effect on the formation of volatile compounds from the thermal degradation of methionine or methionine sulfoxide.Keywords: Methionine; methionine sulfoxide; methional; methyl sulfides; volatiles

SYNTHESIS OF NITROGEN CONTAINING HETEROCYCLES OVER COPPER CHROMITE

The reactions of 1,2-diaminopropane, 1-amino-2-propanol, 1-amino-2-ethanol, and N-(β-aminoethyl)-1,2-diaminoethane in the gas phase over copper chromite have been investigated with the objective of synthesising nitrogen containing heterocycles.At 240-360

EFFECT OF TIME AND TEMPERATURE ON THE PREPARATION OF PYRAZINES IN MODEL REACTIONS OF THE SYNTHESIS OF AROMA-FORMING SUBSTANCES

The qualitative and quantitative compositions of pyrazines that form in model glucose-ammonia and glucose-ammonia-leucine reactions in a glycerol medium were studied.Reaction conditions were found that ensure the synthesis of 23 alkylpyrazines in total concentration ca. 6 g/kg.The obtained mixture of pyrazines is promising for use in the development of food aroma-forming substances.Keywords: pyrazines, Maillard reaction, capillary gas chromatography.

Regioselective Synthesis of Alkylpyrazines

A new, regioselective synthesis of alkylpyrazines begins with condensation of α-oximido carbonyl compounds with allylamines.The resulting imines are isomerized in the presence of potassium tert-butoxide to the corresponding 1-hydroxy-1,4-diazahexatrienes.Thermal electrocyclization-aromatization to pyrazines is best performed after O-acylation of the oximes with methyl chloroformate.