Valerolactam

Structural formula
General
Surname	Valerolactam
other names	2-piperidone; Piperidin-2-one; 2-azacycloxexanone;
Molecular formula	C 5 H 9 NO
Brief description	white to slightly yellow crystals
External identifiers / databases
EC number	211-622-9
ECHA InfoCard	100.010.567
PubChem	12665
Wikidata	Q4596918
properties
Molar mass	99.13 g mol −1
Physical state	firmly
density	1.073 g cm −3
Melting point	38-40 ° C ; 35-39 ° C ;
boiling point	256 ° C ; 255-257 ° C ;
solubility	soluble in water (291 g l −1 at 25 ° C), soluble in ethanol and diethyl ether
safety instructions
GHS labeling of hazardous substances Caution
H and P phrases	H: 319-335
	P: 261-280-305 + 351 + 338
Toxicological data	> 3000 mg kg −1 ( LD 50 , rat , iv )
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Valerolactam (more precisely δ-valerolactam or 2-piperidone) is the lactam of 5-aminovaleric acid (5-aminopentanoic acid), while the positional isomers 3-piperidone and 4-piperidone represent aminoketones.

New biotechnological processes deliver the non-proteinogenic ω- amino acid 5-aminovaleric acid in good yields and thus open up direct and indirect (via δ-valerolactam) access to the so far little investigated polyvalerolactam (polyaminovalerate, polyamide 5).

Manufacturing

When activated with 2-nitrophenyl thiocyanate and tributylphosphine in dimethylformamide at room temperature, 5-aminovaleric acid reacts in an intramolecular cyclization with elimination of water with 73 percent yield to form δ-valerolactam.

The cyclization of 5-aminovaleric acid can also take place enzymatically . In the future, δ-valerolactam from biotechnologically produced 5-aminovaleric acid could be available inexpensively in industrially useful quantities via this route.

When the ammonium salt of 5-aminovaleric acid is heated, δ-valerolactam is also formed.

The conversion of polymers of δ-valerolactone in N-methylpyrrolidone with ammonia at 330 ° C. and a hydrogen pressure of 280 bar produces 2-piperidone in yields of up to 83%.

The hydrogenation of glutarimide in a high pressure autoclave gives δ-valerolactam in yields of up to 70% at 270 ° C. and 490 atm. Hydrogen pressure in the presence of a nickel catalyst

While these manufacturing routes have not found industrial application, the Beckmann rearrangement of cyclopentanone oxime (from cyclopentanone and hydroxylamine ) is a useful method for producing larger quantities of δ-valerolactam.

The rearrangement of the cyclopentanone oxime proceeds faster in the vapor phase on acidic zeolite catalysts than the reaction of the homologous cyclohexanone oxime , which the authors attribute to the greater diffusion of the smaller molecule cyclopentanone oxime into the micropores of the catalyst.

Under mild conditions, the acid-catalyzed rearrangement of cyclopentanone oxime dissolved in ionic liquids achieves very high selectivities (> 99%), but only modest conversions (48%), which is due to the hindrance of the rearrangement due to the higher ring tension in the cyclopentane ring (compared to Cyclohexane homologues).

The gold-catalyzed oxidation of piperidine in toluene gives δ-valerolactam in yields of approx. 60%.

properties

During the synthesis, δ-valerolactam is usually obtained as a yellow-brown and hygroscopic solid. After passing a 50 percent aqueous solution through an acidic ion exchanger , it can be isolated in the form of odorless white crystals, the purity of which also makes them suitable for polymerization to polyvalerolactam.

Applications

After activation with trifluoromethanesulfonic anhydride , the activated δ-valerolactam reacts with amino acids protected on the carboxy group to form dipeptides of ω-amino acids.

N-acylvalerolactams formed by acylation of δ-valerolactam with long-chain aliphatic or aromatic carboxylic acids are suitable as bleach activators .

N-nonanoylvalerolactam (bleach activators)

The anionic polymerization of δ-valerolactam produces polyamide 5 (nylon 5) analogously to the homologous ε-caprolactam .

Polyamides with an odd number of carbon numbers have ferroelectric properties and polarized films made from them show piezoelectric properties that are comparable to those of polyvinylidene fluoride PVDF and make nylon 5 and its copolymers particularly interesting for sensor applications.

Individual evidence

↑ ^a ^b ^c ^d data sheet δ-valerolactam 98% from Sigma-Aldrich , accessed on April 28, 2015 ( PDF ).
↑ ^a ^b ^c ^d ^e ^f data sheet δ-valerolactam 99% at Acros, accessed on July 18, 2019.
↑ ^a ^b Data sheet delta-valerolactam 98% from AlfaAesar, accessed on April 28, 2015 ( PDF )(JavaScript required) .
↑ SJ Park, EY Kim, W. Noh, HM Park, YH Oh, SH Lee, BK Song, J. Jegal, SY Lee: Metabolic engineering of Escherichia coli for the production of 5-aminovalerate and glutarate as C5 platform chemicals . In: Metabolic Engineering . tape 16 , 2013, p. 42-47 , doi : 10.1016 / j.ymben.2012.11.011 .
^ PA Grieco, DS Clark, GP Withers: Direct conversion of carboxylic acids into amides . In: J. Org. Chem. Band 44 , no. 16 , 1979, pp. 2945-2947 , doi : 10.1021 / jo01330a028 .
↑ E. Stavila, K. Loos: Synthesis of lactams using enzyme-catalyzed aminolysis . In: Tetrahedron Lett. tape 54 , 2013, p. 370–373 , doi : 10.1016 / j.tetlet.2012.10.133 .
↑ Patent EP0670311A2 : Process for the production of piperid-2-one. Filed on February 10, 1995 , published on September 6, 1995 , Applicant: BASF AG, inventor L. Franz.
↑ Patent US3745164 : Preparation of butyrolactam and valerolactam. Applied on August 28, 1970 , published July 10, 1973 , applicant: Du Pont of Canada, Ltd., inventor: EG Adamek. ‌
↑ T. Takahashi, K. Ueno, T. Kai: Vapor phase Beckmann rearrangement of cyclopentanone oxime over high silica HZSM-5 zeolites . In: Microporous Materials . tape 1 , no. 5 , 1993, p. 323-327 , doi : 10.1016 / 0927-6513 (93) 80048-Y .
^ S. Guo, Y. Deng: Environmentally friendly Beckmann rearrangement of oximes catalyzed by metaboric acid in ionic liquids . In: Catal. Commun. tape 6 , 2005, p. 225–228 , doi : 10.1016 / j.catcom.2005.01.003 .
↑ Patent US8212027B1 : Process for the conversion of cyclic amines into lactams. Filed April 27, 2011 , published July 3, 2012 , applicant: Iowa State University Research Foundation, Inc., inventor: LK Woo, RJ Angelici. ‌
↑ Patent US2828307 : Process for purification of lactams. Applied on June 26, 1956 , published March 25, 1958 , Applicant: Stamicarbon NV, Inventor: JC Soeterbroek, JA Zeegers. ‌
↑ N. Kuhnert, I. Clemens, R. Walsh: On the activation of valerolactam with triflic anhydride: the synthesis of ω-trifluorosulfonamido dipeptides using a transpeptidation reaction under mild conditions . In: Org. Biomol. Chem. Band 3 , 2005, p. 1694-1701 , doi : 10.1039 / B417779G .
↑ Patent US5405413 : Bleaching compounds comprising acyl valerolactam bleach activators. Filed June 24, 1993 , published April 11, 1995 , Applicant: The Procter & Gamble Co., Inventors: AD Willey, ME Burns, S. Tsunetsugu. ‌
^ JI Scheinbeim, BA Newman: Recent advances in ferroelectric polymers . In: Macromol. Sympos. tape 98 , no. 1 , 1995, p. 897-898 , doi : 10.1002 / masy.19950980178 .

[Sigma-1] ta sheet δ-valerolactam 98% from Sigma-Aldrich , accessed on April 28, 2015 ( PDF ).

[Acros-2] ↑ ^a ^b ^c ^d ^e ^f data sheet δ-valerolactam 99% at Acros, accessed on July 18, 2019.

[Alfa_Aesar-3] Data sheet delta-valerolactam 98% from AlfaAesar, accessed on April 28, 2015 ( PDF )(JavaScript required) .

[4] SJ Park, EY Kim, W. Noh, HM Park, YH Oh, SH Lee, BK Song, J. Jegal, SY Lee: Metabolic engineering of Escherichia coli for the production of 5-aminovalerate and glutarate as C5 platform chemicals . In: Metabolic Engineering . tape 16 , 2013, p. 42-47 , doi : 10.1016 / j.ymben.2012.11.011 .

[5] PA Grieco, DS Clark, GP Withers: Direct conversion of carboxylic acids into amides . In: J. Org. Chem. Band 44 , no. 16 , 1979, pp. 2945-2947 , doi : 10.1021 / jo01330a028 .

[6] E. Stavila, K. Loos: Synthesis of lactams using enzyme-catalyzed aminolysis . In: Tetrahedron Lett. tape 54 , 2013, p. 370–373 , doi : 10.1016 / j.tetlet.2012.10.133 .

[7] Patent EP0670311A2 : Process for the production of piperid-2-one. Filed on February 10, 1995 , published on September 6, 1995 , Applicant: BASF AG, inventor L. Franz.

[8] Patent US3745164 : Preparation of butyrolactam and valerolactam. Applied on August 28, 1970 , published July 10, 1973 , applicant: Du Pont of Canada, Ltd., inventor: EG Adamek. ‌

[9] T. Takahashi, K. Ueno, T. Kai: Vapor phase Beckmann rearrangement of cyclopentanone oxime over high silica HZSM-5 zeolites . In: Microporous Materials . tape 1 , no. 5 , 1993, p. 323-327 , doi : 10.1016 / 0927-6513 (93) 80048-Y .

[10] S. Guo, Y. Deng: Environmentally friendly Beckmann rearrangement of oximes catalyzed by metaboric acid in ionic liquids . In: Catal. Commun. tape 6 , 2005, p. 225–228 , doi : 10.1016 / j.catcom.2005.01.003 .

[11] Patent US8212027B1 : Process for the conversion of cyclic amines into lactams. Filed April 27, 2011 , published July 3, 2012 , applicant: Iowa State University Research Foundation, Inc., inventor: LK Woo, RJ Angelici. ‌

[12] Patent US2828307 : Process for purification of lactams. Applied on June 26, 1956 , published March 25, 1958 , Applicant: Stamicarbon NV, Inventor: JC Soeterbroek, JA Zeegers. ‌

[13] N. Kuhnert, I. Clemens, R. Walsh: On the activation of valerolactam with triflic anhydride: the synthesis of ω-trifluorosulfonamido dipeptides using a transpeptidation reaction under mild conditions . In: Org. Biomol. Chem. Band 3 , 2005, p. 1694-1701 , doi : 10.1039 / B417779G .

[14] Patent US5405413 : Bleaching compounds comprising acyl valerolactam bleach activators. Filed June 24, 1993 , published April 11, 1995 , Applicant: The Procter & Gamble Co., Inventors: AD Willey, ME Burns, S. Tsunetsugu. ‌

[15] JI Scheinbeim, BA Newman: Recent advances in ferroelectric polymers . In: Macromol. Sympos. tape 98 , no. 1 , 1995, p. 897-898 , doi : 10.1002 / masy.19950980178 .