Morpholine

Morpholine^[1]

Names
Preferred IUPAC name Morpholine
Other names Diethylenimide oxide 1,4-Oxazinane Tetrahydro-1,4-oxazine Diethylene imidoxide Diethylene oximide Tetrahydro-p-oxazine
Identifiers
CAS Number	110-91-8 Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:34856 Y
ChemSpider	13837537 Y
ECHA InfoCard	100.003.469
KEGG	C14452 Y
RTECS number	QD6475000
UNII	8B2ZCK305O Y
InChI InChI=1S/C4H9NO/c1-3-6-4-2-5-1/h5H,1-4H2 Y Key: YNAVUWVOSKDBBP-UHFFFAOYSA-N Y InChI=1/C4H9NO/c1-3-6-4-2-5-1/h5H,1-4H2 Key: YNAVUWVOSKDBBP-UHFFFAOYAU
SMILES C1CNCCO1
Properties
Chemical formula	C4H9NO
Molar mass	87.12 g·mol−1
Appearance	Colorless liquid
Odor	Weak ammonia-like or fish-like[2]
Density	1.007 g/cm3
Melting point	−5 °C (23 °F; 268 K)
Boiling point	129 °C (264 °F; 402 K)
Solubility in water	miscible
Vapor pressure	6 mmHg (20 °C)[2]
Acidity (pKa)	8.36[3] (of conjugate acid)
Magnetic susceptibility (χ)	-55.0·10−6 cm3/mol
Hazards
Main hazards	Flammable, Corrosive
Safety data sheet	hazard.com
R-phrases (outdated)	R10 R20/21/22 R34
S-phrases (outdated)	(S1/2) S23 S36 S45
NFPA 704	3 3 0
Flash point	31 °C (88 °F; 304 K)
Autoignition temperature	275 °C (527 °F; 548 K)
Explosive limits	1.4%–11.2%[2]
Lethal dose or concentration (LD, LC):
LD50 (median dose)	1220 mg/kg (mammal, oral) 525 mg/kg (mouse, oral) 1050 mg/kg (rat, oral)[4]
LC50 (median concentration)	365 ppm (mouse, 2 hr)[4]
US health exposure limits (NIOSH):
PEL (Permissible)	TWA 20 ppm (70 mg/m3) [skin][2]
REL (Recommended)	TWA 20 ppm (70 mg/m3) ST 30 ppm (105 mg/m3) [skin][2]
IDLH (Immediate danger)	1400 ppm[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Morpholine is an organic chemical compound having the chemical formula O(CH₂CH₂)₂NH. This heterocycle features both amine and ether functional groups. Because of the amine, morpholine is a base; its conjugate acid is called morpholinium. For example, treating morpholine with hydrochloric acid makes the salt morpholinium chloride.

Production

Morpholine may be produced by the dehydration of diethanolamine with sulfuric acid:^[5]

Uses

Industrial applications

Morpholine is a common additive, in parts per million concentrations, for pH adjustment in both fossil fuel and nuclear power plant steam systems. Morpholine is used because its volatility is about the same as water, so once it is added to the water, its concentration becomes distributed rather evenly in both the water and steam phases. Its pH-adjusting qualities then become distributed throughout the steam plant to provide corrosion protection. Morpholine is often used in conjunction with low concentrations of hydrazine or ammonia to provide a comprehensive all-volatile treatment chemistry for corrosion protection for the steam systems of such plants. Morpholine decomposes reasonably slowly in the absence of oxygen at the high temperatures and pressures in these steam systems.

Organic synthesis

Morpholine undergoes most chemical reactions typical for other secondary amines, though the presence of the ether oxygen withdraws electron density from the nitrogen, rendering it less nucleophilic (and less basic) than structurally similar secondary amines such as piperidine. For this reason, it forms a stable chloramine (CAS#23328-69-0).^[6]

It is commonly used to generate enamines.^[7]

Morpholine is widely used in organic synthesis. For example, it is a building block in the preparation of the antibiotic linezolid, the anticancer agent gefitinib (Iressa) and the analgesic dextromoramide.

In research and in industry, the low cost and polarity of morpholine lead to its common use as a solvent for chemical reactions.

Producers

Most (as above) is widespread in Europe and the USA; accordingly, producers in Europe and the USA are able to cover the domestic and export markets.

Agriculture

As a fruit coating

Morpholine is used as a chemical emulsifier in the process of waxing fruit. Naturally, fruits make waxes to protect against insects and fungal contamination, but this can be lost as the fruit is cleaned. A small amount of new wax is applied to replace it. Morpholine is used as an emulsifier and solubility aid for shellac, which is used as a wax for fruit coating.^[8] The European Union has forbidden the use of morpholine in fruit coating.^[9][10]

As a component in fungicides

Morpholine derivatives used as agricultural fungicides in cereals are known as ergosterol biosynthesis inhibitors.

• Amorolfine
• Fenpropimorph
• Tridemorph

See also

• Morpholino

References

1. ↑ National Institute for Occupational Safety and Health (2000). "Morpholine". International Chemical Safety Cards. Retrieved 5 November 2005. 
2. 1 2 3 4 5 6 "NIOSH Pocket Guide to Chemical Hazards #0437". National Institute for Occupational Safety and Health (NIOSH). 
3. ↑ Hall, H. K. (1957). J. Am. Chem. Soc. 79 (20): 5441. doi:10.1021/ja01577a030.  Missing or empty |title= (help)
4. 1 2 "Morpholine". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH). 
5. ↑ Weissermel, Klaus; Arpe, Hans-Jürgen; Lindley, Charlet R.; Hawkins, Stephen (2003). "Chapter 7. Oxidation Products of Ethylene". Industrial Organic Chemistry. Wiley-VCH. pp. 159–161. ISBN 3-527-30578-5. 
6. ↑ Lindsay Smith, J. R.; McKeer, L. C.; Taylor, J. M. (1993). "4-Chlorination of Electron-Rich Benzenoid Compounds: 2,4-Dichloromethoxybenzene". Org. Synth. ; Coll. Vol., 8, p. 167 
7. ↑ Noyori, R.; Yokoyama, K.; Hayakawa, Y. (1988). "Cyclopentenones from α,α′-Dibromoketones and Enamines: 2,5-Dimethyl-3-Phenyl-2-Cyclopenten-1-one". Org. Synth. ; Coll. Vol., 6, p. 520 
8. ↑ McGuire, Raymond G.; Dimitroglou, Dimitrios A. (1999). "Evaluation of Shellac and Sucrose Ester Fruit Coating Formulations that Support Biological Control of Post-harvest Grapefruit Decay". Bio-control Science and Technology. 9 (1): 53–65. 
9. ↑ "Morpholine". Scientific Analysis Laboratories Ltd. 
10. ↑ "Morpholine Issues in the United Kingdom". Northwest Horticultural Council. September 28, 2010.