Lime oxide

Limonene oxides (also dipentene oxides ) are the name of certain chemical compounds that are derived from limonenes and are formed from these substances through oxidation . Chemically, they are cyclic ethers of monoterpenes . Several limonene oxides are allergenic and jointly responsible for the allergy-promoting effects of many essential oils and the monoterpenes they contain.

The content of lime oxides in essential oils of citrus species increases within a few weeks after extraction and at room temperature. The increase in the level of limonene oxide in caraway seed oil is accelerated by both heat and light.

Members of the substance group

1,8-cineole

cis - D -, cis - L -, trans - D - and trans - L -lime 1,2-oxide

Limonene-1,2: 8,9-dioxide - mixture of several stereoisomers

Lime oxides include

Limonene-1,8-monoxide , see 1,8-cineole
Limonene-1,2-monoxide (LMO) are intermediate products in the synthesis of carveol and carvone :
- cis - (+) - and trans - (+) - limonene-1,2-oxide ( CAS number 1195-92-2), two allergens from the oxidation of D - (+) - limonene. Colorless liquids, irritating to the eyes and skin, with a slight citrus odor and a boiling point of 74 to 75 ° C ( cis ) and 77 ° C ( trans ), or 113–114 ° C at 67 mbar. The density is 0.93 g / ml.
- cis - (-) - and trans - (-) - limonene-1,2-oxide, from the oxidation of L - (-) - limonene
Limonene-1,2: 8,9-dioxide (LDO, CAS number 96-08-2) are also colorless liquids with a slight citrus odor. They have a boiling point of 242 ° C and a density of 1.03 g / ml. They are used to reduce the viscosity of epoxy resins .

Manufacturing

A limonene 1,2-oxide racemate is produced simply via acid-catalyzed oxidation of the corresponding limonene with air or with the help of peracids such as peracetic acid . In the stereospecific synthesis of limonene-1,2-oxides one makes use of asymmetries of various reactions in addition to fractional distillation. For example, the rearrangement of the two D- limonene-1,2-oxides to the corresponding dihydrocarvone proceeds at different speeds and by terminating the reaction, almost pure trans isomer can be retained.

The oxidation of limonene with N -sulfonyloxaziridine is doubly asymmetric; while D- limonene gives almost equal proportions in the racemate, the reaction of L- limonene is strongly enantioselective:

pharmacology

Limonene oxides increase the rate of absorption of haloperidol by the human epidermis; the mechanism seems to be the aggressive behavior of the oxides towards the skin layers.

Individual evidence

↑ AT Karlberg et al .: Air oxidation of d-limonene (the citrus solvent) creates potent allergens. In: Contact Dermatitis . 26/5/ 1992 , pp 332-340; PMID 1395597 .
↑ M. Matura et al .: Not only oxidized R - (+) - but also S - (-) - limonene is a common cause of contact allergy in dermatitis patients in Europe. In: Contact Dermatitis . 55/5/ 2006 , pp 274-279; PMID 17026692 .
^ Q. Wei et al .: Toxicity study of the volatile constituents of Myoga utilizing acute dermal irritation assays and the Guinea-pig Maximization test. In: J Occup Health . 48/6/ 2006 , pp 480-486; PMID 17179641 .
↑ BM Hausen et al .: Degradation products of monoterpenes are the sensitizing agents in tea tree oil. In: American Journal of Contact Dermatitis . 10/2/ 1999 , pp 68-77; PMID 10357714 .
↑ MA Bergstrom et al .: Conjugated dienes as prohaptens in contact allergy: in vivo and in vitro studies of structure-activity relationships, sensitizing capacity, and metabolic activation. In: Chemical Research in Toxicology 2006 , Volume 19, pp. 760-769; PMID 16780354 .
↑ HS Choi and M. Sawamura: Effects of storage conditions on the composition of Citrus tamurana Hort. ex Tanaka (hyuganatsu) essential oil. In: Bioscience, Biotechnology, and Biochemistry . 66/2/ 2002 . Pp. 439-443. PMID 11999424
↑ AM Spanier (ed.): Food Flavors and Chemistry. Advances of the New Millennium. RSC Publishing. 2001 , ISBN 0-85404-875-8 . P. 518 ff.
↑ Patent US6835686 : Catalyst system and process for rearrangement of epoxides to allylic alcohols. Published December 28, 2004 , Inventors: Gennadiy G. Kolomeyer, Jacob S. Oyloe. ‌
↑ Limonene oxide data sheet at Acros, accessed on February 19, 2010.
↑ Patent US3073792 : Composition comprising epoxypolybutadiene and limonene diepoxide. Published January 15, 1963 , inventor: Frank P. Greenspan. ‌
↑ Data sheet from Arkema ( Memento from November 19, 2012 in the Internet Archive ) (PDF; 68 kB).
↑ Patent US3014929 : Method of making carvomenthene oxide. Published December 26, 1961 , Inventors: Frank P. Greenspan, Seymour M. Linder. ‌
↑ Patent US4296257 : Process for producing dihydrocarvone geometric isomers. Published October 20, 1981 , Inventors: Carlos G. Cardenas, Zia U. Din. ‌
↑ T. Katsuki (Ed.): Asymmetric Oxidation Reactions: a practical approach in chemistry. Oxford Univ. Press. 2001 , ISBN 0-19-850201-X , pp. 48-49.
↑ HK Vaddi et al .: Oxide terpenes as human skin penetration enhancers of haloperidol from ethanol and propylene glycol and their modes of action on stratum corneum. In: Biol Pharm Bull . 26/2/ 2003 , pp 220-228; PMID 12576684 .

[1] AT Karlberg et al .: Air oxidation of d-limonene (the citrus solvent) creates potent allergens. In: Contact Dermatitis . 26/5/ 1992 , pp 332-340; PMID 1395597 .

[2] M. Matura et al .: Not only oxidized R - (+) - but also S - (-) - limonene is a common cause of contact allergy in dermatitis patients in Europe. In: Contact Dermatitis . 55/5/ 2006 , pp 274-279; PMID 17026692 .

[3] Q. Wei et al .: Toxicity study of the volatile constituents of Myoga utilizing acute dermal irritation assays and the Guinea-pig Maximization test. In: J Occup Health . 48/6/ 2006 , pp 480-486; PMID 17179641 .

[4] BM Hausen et al .: Degradation products of monoterpenes are the sensitizing agents in tea tree oil. In: American Journal of Contact Dermatitis . 10/2/ 1999 , pp 68-77; PMID 10357714 .

[5] MA Bergstrom et al .: Conjugated dienes as prohaptens in contact allergy: in vivo and in vitro studies of structure-activity relationships, sensitizing capacity, and metabolic activation. In: Chemical Research in Toxicology 2006 , Volume 19, pp. 760-769; PMID 16780354 .

[6] HS Choi and M. Sawamura: Effects of storage conditions on the composition of Citrus tamurana Hort. ex Tanaka (hyuganatsu) essential oil. In: Bioscience, Biotechnology, and Biochemistry . 66/2/ 2002 . Pp. 439-443. PMID 11999424

[7] AM Spanier (ed.): Food Flavors and Chemistry. Advances of the New Millennium. RSC Publishing. 2001 , ISBN 0-85404-875-8 . P. 518 ff.

[8] Patent US6835686 : Catalyst system and process for rearrangement of epoxides to allylic alcohols. Published December 28, 2004 , Inventors: Gennadiy G. Kolomeyer, Jacob S. Oyloe. ‌

[9] Limonene oxide data sheet at Acros, accessed on February 19, 2010.

[10] Patent US3073792 : Composition comprising epoxypolybutadiene and limonene diepoxide. Published January 15, 1963 , inventor: Frank P. Greenspan. ‌

[11] Data sheet from Arkema ( Memento from November 19, 2012 in the Internet Archive ) (PDF; 68 kB).

[12] Patent US3014929 : Method of making carvomenthene oxide. Published December 26, 1961 , Inventors: Frank P. Greenspan, Seymour M. Linder. ‌

[13] Patent US4296257 : Process for producing dihydrocarvone geometric isomers. Published October 20, 1981 , Inventors: Carlos G. Cardenas, Zia U. Din. ‌

[14] T. Katsuki (Ed.): Asymmetric Oxidation Reactions: a practical approach in chemistry. Oxford Univ. Press. 2001 , ISBN 0-19-850201-X , pp. 48-49.

[15] HK Vaddi et al .: Oxide terpenes as human skin penetration enhancers of haloperidol from ethanol and propylene glycol and their modes of action on stratum corneum. In: Biol Pharm Bull . 26/2/ 2003 , pp 220-228; PMID 12576684 .