80-59-1

Basic information

• Product Name: Tiglic acid
• Synonyms: (E)-2-METHYL-2-BUTENOIC ACID;E-2,3-DIMETHYLACRYLIC ACID;FEMA 3599;2,3-DIMETHYLACRYLIC ACID;2-METHYL-TRANS-2-BUTENOIC ACID;2-METHYL-2-BUTENOIC ACID;2-METHYLBUT-2-ENOIC ACID;2-METHYLCROTONIC ACID
• CAS NO: 80-59-1
• Molecular Formula: C₅H₈O₂
• Molecular Weight: 100.12
• EINECS: 201-295-0
• Product Categories: Aromatic Cinnamic Acids, Esters and Derivatives
• Mol File: 80-59-1.mol
• Article Data: 33

Chemical Properties

• Melting Point: 61-64 °C(lit.)
• Boiling Point: 95-96 °C12 mm Hg(lit.)
• Flash Point: 101°C
• Appearance: White to beige/Crystalline Powder and Chunks
• Density: 0.969 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.152mmHg at 25°C
• Refractive Index: nD81 1.4342
• Storage Temp.: Refrigerator (+4°C)
• PKA: pK (25°) 5.02
• Water Solubility: SOLUBLE IN HOT WATER
• Merck: 14,9433
• BRN: 1236500
• CAS DataBase Reference: Tiglic acid(CAS DataBase Reference)
• NIST Chemistry Reference: Tiglic acid(80-59-1)
• EPA Substance Registry System: Tiglic acid(80-59-1)

Safety Data

• Hazard Codes: C,Xi
• Statements: 34-36/37/38
• Safety Statements: 26-36/37/39-45-24/25-27
• RIDADR: UN 3261 8/PG 2
• WGK Germany: 2
• RTECS: GQ5430000
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 80-59-1(Hazardous Substances Data)

Usage

Description

Different sources of media describe the Description of 80-59-1 differently. You can refer to the following data:
1. Tiglic acid (also (E)-2-Methylbut-2-enoic acid) is an organic acid. It occurs in croton oil, Roman chamomile, and geranium. It can be prepared by dehydration of MEK cyanohydrin, followed by the hydrolysis of the nitrile function. It is either in the form of a thick syrup or colorless crystals.? It is with a sweet, warm, spicy odor. It is used to synthesize esters for perfume manufacturing industry and as a raw material to produce acids and esters, which are applied as flavoring agent for food and beverage industry. Tiglic acid is also a useful starting material in the synthesis of pharmaceutical intermediates.
2. frarc.s-2-Methyl-2-butenoic acid has a sweet, warm, spicy odor. May be synthesized from 2-hydroxy-2-methylbutyronitrile.

References

[1] H. Panda (2010) Perfumes and Flavours Technology Handbook. [2] Paul T. Anastas (2009) Handbook of Green Chemistry, Green Catalysis, Biocatalysis. [3] https://en.wikipedia.org/wiki/Tiglic_acid

Chemical Properties

trans-2-Methyl-2-butenoic acid has a sweet, warm, spicy odor.

Occurrence

Reported found in celery leaves and stalk, cocoa, mango, dried bonito and Roman chamomile oil

Uses

Tiglic acid is the stable isomer of angelic acid. Tiglic acid was found as glyceride in croton oil, as butyl ester in the oil of the Roman camomile, and as geranyl tiglate in oil of geranium. Tiglic a cid is formed during the charcoaling of maple wood.

Definition

ChEBI: A 2-methylbut-2-enoic acid having its double bond in trans-configuration.

Taste threshold values

Taste characteristics at 75 ppm: sweet, brown, fruity, with ripe and jamy nuances.

General Description

A white lustrous flaked solid with a fruity or spicy odor. About the same density as water and slightly soluble in water. May burn if heated to high temperatures. May severely irritate skin, eyes, lungs or mucous membranes.

Air & Water Reactions

Slightly soluble in water.

Reactivity Profile

TIGLIC ACID is a carboxylic acid. Carboxylic acids donate hydrogen ions if a base is present to accept them. They react in this way with all bases, both organic (for example, the amines) and inorganic. Their reactions with bases, called "neutralizations", are accompanied by the evolution of substantial amounts of heat. Neutralization between an acid and a base produces water plus a salt. Carboxylic acids in aqueous solution and liquid or molten carboxylic acids can react with active metals to form gaseous hydrogen and a metal salt. Such reactions occur in principle for solid carboxylic acids as well, but are slow if the solid acid remains dry. Even "insoluble" carboxylic acids may absorb enough water from the air and dissolve sufficiently in Tiglic acid to corrode or dissolve iron, steel, and aluminum parts and containers. Carboxylic acids, like other acids, react with cyanide salts to generate gaseous hydrogen cyanide. The reaction is slower for dry, solid carboxylic acids. Insoluble carboxylic acids react with solutions of cyanides to cause the release of gaseous hydrogen cyanide. Flammable and/or toxic gases and heat are generated by the reaction of carboxylic acids with diazo compounds, dithiocarbamates, isocyanates, mercaptans, nitrides, and sulfides. Carboxylic acids, especially in aqueous solution, also react with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (SO2), to generate flammable and/or toxic gases and heat. Their reaction with carbonates and bicarbonates generates a harmless gas (carbon dioxide) but still heat. Like other organic compounds, carboxylic acids can be oxidized by strong oxidizing agents and reduced by strong reducing agents. These reactions generate heat. A wide variety of products is possible. Like other acids, carboxylic acids may initiate polymerization reactions; like other acids, they often catalyze (increase the rate of) chemical reactions.

Health Hazard

TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

Fire Hazard

Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Some are oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated.

Safety Profile

Low toxicity by ingestion and skin contact. A severe skin irritant. When heated to decomposition it emits acrid smoke and irritating fumes.

Synthesis

Synthesized from 2-hydroxy-2-methylbutyronitrile

Purification Methods

Crystallise it from water. It is steam volatile and is soluble in organic solvents. [Beilstein 2 IV 1552.]

InChI:InChI=1/C5H8O2/c1-3-4(2)5(6)7/h3H,1-2H3,(H,6,7)/b4-3-

Synthetic route

(S)-12-hydroxypentadecanoic acid 12-O-(6-O-(S)-2-methylbutyryl)-β-D-glucopyranosyl-(1->3)-O-[4-O-tigloyl-α-L-rhamnopyranosyl-(1->4)]-O-[2-O-(S)-2-methylbutyryl]-α-L-rhamnopyranosyl-(1->4)-O-α-L-rhamnopyranosyl-(1->2)-β-D-glucopyranoside (1400908-83-9) → 2-Methylbutanoic acid (116-53-0, 600-07-7) + Tiglic acid (80-59-1) + (S)-12-hydroxypentadecanoic acid 12-O-β-D-glucopyranosyl-(1->3)-O-[α-L-rhamnopyranosyl-(1->4)]-O-α-L-rhamnopyranosyl-(1->4)-O-α-L-rhamnopyranosyl-(1->2)-β-D-glucopyranoside (1400908-78-2)

Conditions	Yield
With potassium hydroxide at 85℃; for 4h; pH=4;	A 98% B 98% C 3 mg

turpethoside acid B (1400908-85-1) → 2-Methylbutanoic acid (116-53-0, 600-07-7) + Tiglic acid (80-59-1) + (S)-12-hydroxyhexadecanoic acid 12-O-β-D-glucopyranosyl-(1->3)-O-[α-L-rhamnopyranosyl-(1->4)]-O-α-L-rhamnopyranosyl-(1->4)-O-α-L-rhamnopyranosyl-(1->2)-β-D-glucopyranoside (1400908-79-3)

Conditions	Yield
With potassium hydroxide at 85℃; for 4h; pH=4;	A 98% B 98% C 3 mg

(E)-2-bromobut-2-ene (3017-71-8) + carbon monoxide (201230-82-2) → Tiglic acid (80-59-1)

Conditions	Yield
With sodium hydroxide; cetyltrimethylammonim bromide; nickel cyanide In toluene at 95℃; under 735.5 Torr; for 6h;	89%
With calcium hydroxide; methyl iodide; dicobalt octacarbonyl In 1,4-dioxane; water at 20℃; under 760 Torr; for 20h;	88 % Chromat.

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + (E)-2-bromobut-2-ene (3017-71-8) → Tiglic acid (80-59-1)

Conditions	Yield
With calcium hydroxide; carbon monoxide; methyl iodide In 1,4-dioxane; water 20°C, 20 h.;	88%

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + (Z)-2-Bromo-2-butene (3017-68-3) → Tiglic acid (80-59-1)

Conditions	Yield
With calcium hydroxide; carbon monoxide; methyl iodide In 1,4-dioxane; water 20°C, 20 h.;	87%

Cp2TiOOC(trans-C(CH3)=CHCH3) → Tiglic acid (80-59-1)

Conditions	Yield
With water In diethyl ether for 1h; Ambient temperature;	85%

(E)-3-methylpent-3-en-2-one (1567-73-3) → Tiglic acid (80-59-1)

Conditions	Yield
With sodium hypochlorite solution; sodium hydroxide at 55 - 60℃; for 1h; Large scale;	84.3%

2-hydroxy-2-methylbutyric acid (3739-30-8) → Tiglic acid (80-59-1)

Conditions	Yield
With sulfuric acid at 140℃;	76.5%
Erhitzen;
With sulfuric acid at 115 - 130℃; im geschlossenen Rohr;

2-chloro-2-methylbutyric acid (73758-54-0) → Tiglic acid (80-59-1)

Conditions	Yield
With potassium hydroxide In ethanol for 6h; Reflux;	70%

2-methylenebutyric acid (3586-58-1) → Tiglic acid (80-59-1)

Conditions	Yield
With water at 230℃; for 3h;	62%
With sulfuric acid

2-acetylpropanoic acid ethyl ester (609-14-3) → Tiglic acid (80-59-1)

Conditions	Yield
With methanol; calcium borate anschliessend mit methanol. Natronlauge und Erhitzen des nach dem Ansaeuern mit wss. Salzsaeure erhaltenen Reaktionsprodukts in Gegenwart von Toluol-4-sulfonsaeure;
Multi-step reaction with 2 steps 1: sodium amalgam; diluted alcohol / man haelt die Reaktion mit verduennter Schwefelsaeure stets schwach saurer 2: Destillation View Scheme

carbon disulfide (75-15-0) + Angelic acid (565-63-9) → Tiglic acid (80-59-1)

Conditions	Yield
bei Gegenwart von Spuren Brom;in dem direkten Sonnenlicht;

3-methyl-4,5-dihydro-3H-pyrazole-3-carboxylic acid ethyl ester → Tiglic acid (80-59-1) + 1-methylcyclopropanecarboxylic acid ethyl ester (71441-76-4)

Conditions	Yield
at 140℃;

2-methylbut-2-enal (497-03-0) → Tiglic acid (80-59-1)

Conditions	Yield
an der Luft;
Stage #1: 2-methylbut-2-enal With palladium(II) trifluoroacetate at 10℃; for 0.166667h; Stage #2: With dihydrogen peroxide In water at 10℃; chemoselective reaction;	47 %Chromat.

(E)-2-bromobut-2-ene (3017-71-8) → Tiglic acid (80-59-1)

Conditions	Yield
With tetrahydrofuran; magnesium anschliessend mit Kohlendioxid;
With diethyl ether; lithium anschliessend mit Kohlendioxid;

Angelic acid (565-63-9) → Tiglic acid (80-59-1)

Conditions	Yield
Kochen;
at 300℃; im geschlossenen Rohr;
With sulfuric acid at 100℃;

pent-2-enoic acid (626-98-2, 13991-37-2, 16666-42-5) → Tiglic acid (80-59-1) + butanone (78-93-3)

Conditions	Yield
With sulfuric acid

Upstream product

• 75-15-0 carbon disulfide 
• 565-63-9 Angelic acid 
• 4111-08-4 2-hydroxy-2-methyl-butyronitrile 
• 3017-68-3 (Z)-2-Bromo-2-butene 
• 201230-82-2 carbon monoxide 
• 3017-71-8 (E)-2-bromobut-2-ene 
• 3739-30-8 2-hydroxy-2-methylbutyric acid 
• 51060-05-0 fulminic acid 
• 7664-93-9 sulfuric acid 
• 78-93-3 butanone 
• 74-86-2 acetylene 
• 62-59-9 veratrine 
• 3586-58-1 2-methylenebutyric acid 
• 408314-02-3 3-bromo-2-methyl-butyric acid 

Downstream Products

• 6622-76-0 methyl (E)-2-methyl-2-butenoate 
• 5798-88-9 β-bromo-isovaleric acid 
• 13277-92-4 1-methyl-trans-2-methylcyclohexanecarboxylic acid 
• 13277-91-3 (+/-)-cis-1.2-Dimethyl-cyclohexen-⁽⁴⁾-carbonsaeure-⁽¹⁾ 
• 14316-68-8 (E)-2-methyl-2-butenoic anhydride 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 
• 16782-79-9 3,5,6-trimethylcyclohex-2-en-1-one 
• 59082-95-0 2-((1S,2R,3R)-2-Chloro-1,3-dimethyl-cyclopropyl)-propan-2-ol 
• 59082-96-1 2-((1S,2R,3R)-2-Bromo-1,3-dimethyl-cyclopropyl)-propan-2-ol 
• 66788-29-2 1-((1S,2R,3R)-2-Chloro-1,3-dimethyl-cyclopropyl)-ethanone 
• 62234-89-3 (2E,3Z)-2-Acetyl-1-brom-2,3-dimethylcyclopropan 
• 134255-76-8 (E)-2-methyl-1-(2,4,5-trimethoxy-3-methylphenyl)but-2-en-1-one 
• 134255-77-9 (E)-2-Methyl-1-(2,3,5-trimethoxy-4-methyl-phenyl)-but-2-en-1-one 
• 134255-82-6 4,6,7-trimethoxy-1,2,5-trimethyl-1H-inden-3-yl (E)-2'-methylbut-2'-enoate 

Relevant articles and documents

The structure of fexerin

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Method for simply and conveniently synthesizing tiglic acid

The invention discloses a method for simply and conveniently synthesizing tiglic acid. The method comprises the following steps: carrying out an addition reaction between a Grignard reagent and pyruvic acid or alpha-butanone acid at a normal temperature by using HMPA or DMPU as an assistant to obtain 2-hydroxy-2-methylbutyric acid, marking the 2-hydroxy-2-methylbutyric acid as an intermediate III;and then, heating the intermediate III under the action of sulfuric acid with a mass concentration of not less than 67% to carry out dehydration reaction to obtain tiglic acid. Materials which can cause serious pollution in the prior art are not used, the reaction steps are short, the technological conditions are simple, no special requirements for equipment exist, the product yield is high, andthe method is suitable for industrial production.

Industrial preparation method of tiglic acid

The invention discloses an industrial preparation method of tiglic acid. The industrial preparation method is characterized by comprising the following steps: taking sodium acid sulfate as a catalyst,preparing 3-methyl-3-pentene-2-one (formula II) by utilizing paraldehyde and butanone which are cheap and are commercially easily obtained, and carrying out haloform reaction on a compound shown as the formula II, a sodium hypochlorite water solution and a sodium hydroxide water solution in a continuous flowing reactor to prepare the tiglic acid (formula I). By adopting the method, the disadvantages in the prior art are overcome; the method has the advantages that a utilized catalyst is cheap and easy to obtain and has high catalytic activity, no corrosion to equipment and less pollution caused by three wastes; the continuous flowing reactor provides better heat efficiency and has lower energy consumption; meanwhile, compared with a kettle type stirring reactor, production procedures aresimplified, the production time is shortened, the yield of a product is high and the operation is simple; the method is more suitable for industrial production.