11-Aminoundecanoic acid

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11-Aminoundecanoic acid
11-Aminoundecansaure Strukturformel.svg
Names
Preferred IUPAC name
11-Aminoundecanoic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.017.652 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C11H23NO2/c12-10-8-6-4-2-1-3-5-7-9-11(13)14/h1-10,12H2,(H,13,14)
    Key: GUOSQNAUYHMCRU-UHFFFAOYSA-N
  • InChI=1/C11H23NO2/c12-10-8-6-4-2-1-3-5-7-9-11(13)14/h1-10,12H2,(H,13,14)
    Key: GUOSQNAUYHMCRU-UHFFFAOYAM
  • C(CCCCCN)CCCCC(=O)O
Properties
C11H23NO2
Molar mass 201.310 g·mol−1
AppearanceWhite solid
Density 1,1720 g·cm−3
Melting point 188–191 °C (370–376 °F; 461–464 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

11-Aminoundecanoic acid is an organic compound with the formula H2N(CH2)10CO2H. This white solid is classified as an amine and a fatty acid. 11-Aminoundecanoic acid is a precursor to Nylon-11. [1]

Production

As practiced by Arkema, 11-aminoundecanoic acid is prepared industrially from undecylenic acid, which is derived from castor oil. [2] The synthesis proceeds in four separate reactions:

Transesterification of castor oil to methyl ricinoleate

Crude castor oil consists of about 80% triglycerides, from the ricinoleic acid, itself representing about 90% of the oil. [3] It is quantitatively transesterified with methanol to methyl ricinoleate (the methyl ester of ricinoleic acid) in the presence of the basic sodium methoxide at 80 °C within 1 h reaction time in a stirred reactor. At the end of the reaction, the resulting glycerol separates and the liquid methyl ester is washed with water to remove residual glycerol.

Rizinusol-Umesterung Rizinusol-Umesterung.svg
Rizinusöl-Umesterung

Pyrolysis of methylricinoleate to heptanal and methyl undecenoate

Methylricinoleate is evaporated at 250 °C, mixed with hot steam (600 °C) in a 1:1 ratio and decomposed in a cracking furnace at 400 - 575 °C at a retention time of about 10 seconds into its cleavage products heptanal and methyl undecenoate. The cleavage of the aliphatic chain occurs in this variant of the steam cracking selectively between the hydroxymethylene and the allyl-methylene group. Besides heptanal and methyl undecenoate, a mixture of methyl esters of saturated and unsaturated C18-carboxylic acids is obtained. This mixture is known under the trade name Esterol and is used as a lubricant additive.

Pyrolyse von Ricinolsauremethylester Pyrolyse von Ricinolsauremethylester.svg
Pyrolyse von Ricinolsäuremethylester

Hydrolysis of methyl undecenoate to 10-undecenoic acid

The hydrolysis of the methyl ester with sodium hydroxide proceeds at 25 °C within 30 min with quantitative yield. After acidification with hydrochloric acid, solid 10-undecenoic acid (undecylenic acid) is obtained.

Hydrolyse Methylundecenoat.svg

Hydrobromination of 10-undecenoic acid to 11-bromoundecanoic acid

The undecenoic acid is dissolved in toluene and, in the presence of the radical initiator benzoyl peroxide (BPO), gaseous hydrogen bromide is added, in contrary to the Markovnikov rule ("anti-Markovnikov"). When cooled to 0 °C, the fast and highly exothermic reaction produces 11-bromoundecanoic acid in 95% yield - the Markovnikov product 10-bromoundecanoic acid is produced in small quantities as a by-product. Toluene and unreacted hydrogen bromide are extracted under reduced pressure and reused.

Bromundecansaure.svg

Bromine exchange of 11-bromoundecanoic acid to 11-aminoundecanoic acid

11-Bromodecanoic acid is mixed at 30 °C with a large excess of 40% aqueous ammonia solution. When the reaction is complete, water is added and the mixture is heated to 100 °C to remove the excess ammonia.

Synthese von 11-Aminoundecansaure.svg

The acid can be recrystallized from water. For further purification, the hydrochloride of 11-aminoundecanoic acid, which is available by acidification with hydrochloric acid, can be recrystallized from a methanol/ethyl acetate mixture. [4]

Properties

11-Aminoundecanoic acid is a white crystalline and odorless solid with low solubility in water.

Use

By acylation of 11-aminoundecanoic acid with chloroacetyl chloride, chloroacetylamino-11-undecanoic acid can be produced, which acts as a fungicide and insecticide. [5]

N-acyl derivatives of 11-aminoundecanoic acid in the form of oligomeric amides have remarkable properties as gelling agents for water and organic solvents. [6]

Monomer for polyamide 11

By far the most important application of 11-aminoundecanoic acid is its use as a monomer for polyamide 11 (also: nylon-11). Wallace Carothers, the inventor of polyamide (nylon 66), is said to have polymerized 11-aminoundecanoic acid as early as 1931. [7]

Polykondensation von 11-Aminoundecansaure.svg

Although polyamide 11 is derived from a renewable raw material (i.e. biobased), it is not biodegradable. Nevertheless, it has the most advantageous ecological profile of comparable thermoplastics. [8] Due to its excellent toughness at low temperatures, polyamide 11 can be used at temperatures as low as -70 °C. Its relatively non-polar molecular structure due to the low frequency of amide bonds in the molecule results in low moisture absorption compared to polyamide 6 or polyamide 66. In addition, polyamide 11 has very good chemical stability, e.g. against hydrocarbons, low density, good thermal stability, weather resistance and is easy to process.

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. These compounds contain a distinctive functional group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Nylon</span> Early synthetic polymer developed as a textile fibre

Nylon is a family of synthetic polymers with amide backbones, usually linking aliphatic or semi-aromatic groups.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Castor oil</span> Vegetable oil pressed from castor beans

Castor oil is a vegetable oil pressed from castor beans, the seeds of the plant Ricinus communis. The seeds are 40 to 60 percent oil. It is a colourless or pale yellow liquid with a distinct taste and odor. Its boiling point is 313 °C (595 °F) and its density is 0.961 g/cm3. It includes a mixture of triglycerides in which about 90 percent of fatty acids are ricinoleates. Oleic acid and linoleic acid are the other significant components.

Transesterification is the process of exchanging the organic functional group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. Strong acids catalyze the reaction by donating a proton to the carbonyl group, thus making it a more potent electrophile. Bases catalyze the reaction by removing a proton from the alcohol, thus making it more nucleophilic. The reaction can also be accomplished with the help of enzymes, particularly lipases.

A polyamide is a polymer with repeating units linked by amide bonds.

<span class="mw-page-title-main">Step-growth polymerization</span> Type of polymerization reaction mechanism

In polymer chemistry, step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally-occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands. There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place.

In organic chemistry, a dicarboxylic acid is an organic compound containing two carboxyl groups. The general molecular formula for dicarboxylic acids can be written as HO2C−R−CO2H, where R can be aliphatic or aromatic. In general, dicarboxylic acids show similar chemical behavior and reactivity to monocarboxylic acids.

Enanthic acid, also called heptanoic acid, is an organic compound composed of a seven-carbon chain terminating in a carboxylic acid functional group. It is a colorless oily liquid with an unpleasant, rancid odor. It contributes to the odor of some rancid oils. It is slightly soluble in water, but very soluble in ethanol and ether. Salts and esters of enanthic acid are called enanthates or heptanoates.

<span class="mw-page-title-main">Polyester</span> Category of polymers, in which the monomers are joined together by ester links

Polyester is a category of polymers that contain one or two ester linkages in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.

Kolliphor EL, formerly known as Cremophor EL, is the registered trademark of BASF Corp. for its version of polyethoxylated castor oil. It is prepared by reacting 35 moles of ethylene oxide with each mole of castor oil. The resulting product is a mixture : the major component is the material in which the hydroxyl groups of the castor oil triglyceride have been ethoxylated with ethylene oxide to form polyethylene glycol ethers. Minor components are the polyethyelene glycol esters of ricinoleic acid, polyethylene glycols and polyethylene glycol ethers of glycerol. Kolliphor EL is a synthetic, nonionic surfactant used to stabilize emulsions of nonpolar materials in water.

<span class="mw-page-title-main">Polyglycerol polyricinoleate</span> Emulsion used in food production

Polyglycerol polyricinoleate (PGPR), E476, is an emulsifier made from glycerol and fatty acids. In chocolate, compound chocolate and similar coatings, PGPR is mainly used with another substance like lecithin to reduce viscosity. It is used at low levels, and works by decreasing the friction between the solid particles in molten chocolate, reducing the yield stress so that it flows more easily, approaching the behaviour of a Newtonian fluid. It can also be used as an emulsifier in spreads and in salad dressings, or to improve the texture of baked goods. It is made up of a short chain of glycerol molecules connected by ether bonds, with ricinoleic acid side chains connected by ester bonds.

Undecylenic acid is an organic compound with the formula CH2=CH(CH2)8CO2H. It is an unsaturated fatty acid. It is a colorless oil. Undecylenic acid is mainly used for the production of Nylon-11 and in the treatment of fungal infections of the skin, but it is also a precursor in the manufacture of many pharmaceuticals, personal hygiene products, cosmetics, and perfumes. Salts and esters of undecylenic acid are known as undecylenates.

<span class="mw-page-title-main">Ricinoleic acid</span> Chemical compound

Ricinoleic acid, formally called 12-hydroxy-9-cis-octadecenoic acid, is a fatty acid. It is an unsaturated omega-9 fatty acid and a hydroxy acid. It is a major component of the seed oil obtained from the seeds of castor plant, the plant that produces ricin. It is also found in the sclerotium of ergot. About 90% of the fatty acid content in castor oil is the ricinolein.

Nylon 11 or Polyamide 11 is a polyamide, bioplastic and a member of the nylon family of polymers produced by the polymerization of 11-aminoundecanoic acid. It is produced from castor beans by Arkema under the trade name Rilsan.

Natural oil polyols, also known as NOPs or biopolyols, are polyols derived from vegetable oils by several different techniques. The primary use for these materials is in the production of polyurethanes. Most NOPs qualify as biobased products, as defined by the United States Secretary of Agriculture in the Farm Security and Rural Investment Act of 2002.

Heptanal or heptanaldehyde is an alkyl aldehyde. It is a colourless liquid with a strong fruity odor, which is used as precursor to components in perfumes and lubricants.

<span class="mw-page-title-main">2-Methylglutaronitrile</span> Chemical compound

2-Methylglutaronitrile is the organic compound with the formula NCCH2CH2CH(CH3)CN. This dinitrile is obtained in the large-scale synthesis of adiponitrile. It is a colorless liquid with an unpleasant odor. It is the starting compound for the vitamin nicotinamide and for the diester dimethyl-2-methylglutarate and the ester amide methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, which are promoted as green solvents. 2-Methylglutaronitrile is chiral but is mainly encountered as the racemate. It is also used to make Dytek A.

Jasminaldehyde is a fine chemical used as an aroma compound in perfumes. It is responsible for jasmine's characteristic scent.

<span class="mw-page-title-main">Diallyl carbonate</span> Acrylating agent

Diallyl carbonate (DAC) is a colorless liquid with a pungent odor. Its structure contains allyl groups and a functional carbonate group. The presence of double bonds in the allyl groups makes it reactive in various chemical processes. This compound plays a key role in the production of polymers, including polycarbonates and polyurethanes. Diallyl carbonate is soluble in ethanol, methanol, toluene, and chloroform. Diallyl carbonate reacts with amines, alcohols, and thiols.

References

  1. Herzog, Ben; Kohan, Melvin I.; Mestemacher, Steve A.; Pagilagan, Rolando U.; Redmond, Kate (2013). "Polyamides". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a21_179.pub3. ISBN   978-3-527-30385-4.
  2. A. Chauvel, G. Lefebvre, Petrochemical Processes: Technical and Economic Characteristics, Band 2, S. 277, Editions Technip, Paris, 1989, ISBN   2-7108-0563-4.
  3. Gupta, S. S.; Hilditch, T. P.; Riley, J. P. (1951). "The fatty acids and glycerides of castor oil". Journal of the Science of Food and Agriculture. 2 (6): 245–251. Bibcode:1951JSFA....2..245G. doi:10.1002/jsfa.2740020603.
  4. Koh, Moo-Hyun; Kim, Hyeon-Jeong; Shin, Na-Ra; Kim, Hyun-Su; Yoo, Dong-Won; and Kim, Young-Gyu (2012). "Divergent Process for C10, C11 and C12 ω-Amino Acid and α,ω-Dicarboxylic Acid Monomers of Polyamides from Castor Oil as a Renewable Resource". Bulletin of the Korean Chemical Society. 33 (6): 1873–1878. doi:10.5012/bkcs.2012.33.6.1873.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. US 4055663,Sol J. Barer et al.,,"Halogenated acylamino acids as fungicides",issued 1977-10-25, assigned to National Patent Development Corp.
  6. d'Aléo, Anthony; Pozzo, Jean-Luc; Fages, Frédéric; Schmutz, Marc; Mieden-Gundert, Gudrun; Vögtle, Fritz; Caplar, Vesna; Zinic, Mladen (2004). "11-Aminoundecanoic acid: A versatile unit for the generation of low molecular weight gelators for water and organic solvents". Chem. Commun. (2): 190–191. doi:10.1039/B307846A. PMID   14737543.
  7. Renewable Polymers: Synthesis, Processing, and Technology, edited by V. Mittal, J. Wiley & Sons, Hoboken, NJ, ISBN   978-0-470-93877-5
  8. Jim Mason: Rilsan Polyamide-11 - A success story for sustainable resource based engineering thermoplastics Archived December 4, 2016, at the Wayback Machine , 9. April 2008.