Vogelzang
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diphenyl ether
Does anyone here know how safe diphenyl ether (aka phenyl ether or diphenyl oxide) is as far as developing peroxides? You can test ethers for
peroxides using KI solution and reduce them use FeSO4 or other reducing agent.
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grind
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Diphenylether should be absolutely safe concerning peroxides. I´ve read alot about peroxides in organic compounds and never heard anything that
diphenylether is affected by that. Another fact, diphenylether does not possess an alpha-H, so peroxid-development shouldn´t be possible.
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Vogelzang
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diphenyl ether is given a (3) rating (may also form peroxides) here: http://policies.anu.edu.au/attachments/714
Strangely enough, it may be used as a stabilizer when distilling other ethers according to
US 2254404 Distillation of ethers containing peroxides
page 1 column 2 line 43 diphenyl oxide as stabilizer
http://www.pat2pdf.org
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From Google books
Perfumery synthetics and isolates - Page 193
by Paul Z. Bedoukian - Perfumes, Synthetic - 1951 - 488 pages
Weight 170.20 Diphenyl oxide has been used by perfumers for many years because
of its strong geranium odor. It has a somewhat crude odor, however, ...
Since diphenyl oxide is an ether, it is extremely stable under all conditions
encountered in the soap, perfume, or cosmetic industry.
[Edited on 23-4-2009 by Vogelzang]
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Ozone
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It may form peroxides but, following scission (homolytic cleavage), can stabilize multiple radicals by delocalizing them within the pi system of each
ring.
Cheers,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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grind
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Quote: Originally posted by Vogelzang  |
Strangely enough, it may be used as a stabilizer when distilling other ethers
[Edited on 23-4-2009 by Vogelzang] |
I think it is rather a dilution agent than a stabilizer in this case. DPE is not as volatile as the usual ethers used as solvents and dilutes the
peroxides which remain after distillation of the ethers. A diluted solution of peroxides is not as explosive as the neat peroxides are.
Of course you can substitute DPE, a lot of less volatile compounds are suitable for this purpose.
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Eclectic
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http://www.dow.com/heattrans/prod/synthetic/dowtherm.htm
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Vogelzang
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US 1882809 Composition of matter
diphenyl oxide & diphenyl eutectic diagram
US 1899257 Process for the purification of diphenyloxide
US 1746977 Electrical apparatus
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Vogelzang
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SOME PROPERTIES OF PHENYL ETHER.
Alfred N. Cook
J. Am. Chem. Soc., 1904, 26 (3), 302-304
Attachment: ja01993a011-phenylether.pdf (185kB)
This file has been downloaded 874 times
[Edited on 25-4-2009 by Vogelzang]
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Vogelzang
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Danger of explosion: Product does not present an explosion hazard.
http://www.alfa.com/content/msds/USA/A15791.pdf
Some links/sources say that diphenyl ether can form explosive mixtures with air, for example:
http://www.fileden.com/files/2008/8/24/2063601/chemistry/JCE...
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Vogelzang
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STUDIES IN AUTO-OXIDATION REACTIONS. II. THE MECHANISM OF THE AUTO-OXIDATION OF CERTAIN ETHERS
Nicholas A. Milas
J. Am. Chem. Soc., 1931, 53 (1), 221-233
http://www.fileden.com/files/2008/8/24/2063601/chemistry/ja0...
THE CHEMISTRY OF THE DIARYL ETHERS
http://www.fileden.com/files/2008/8/24/2063601/chemistry/cr6...
http://www.pat2pdf.org
US 2254404 Distillation of ethers containing peroxides
high boiling hydrocarbon oil as stabilizer
US 2790813 Safe recovery of tetrahydrofuran vapors
US 3003002 Purification of ether
anion exchange resin, KI test for peroxides
US 2552670
reduction of peroxides in cyclic ketones
col. 1 lines 42+
In accordance with the present invention, the peroxides are removed from the oxidation effluent by treatment with an aqueous solution of a reducing
agent, such as a ferrous salt, a stannous salt, a chromous salt, a sulfite, or a bisulfite, that reduces peroxides.
US 2563598
removal of peroxides and similar unstable oxy-compounds from mixtures of hydrocarbons and oxygenated organic compounds
US 3420906 REMOVAL OF PEROXIDES FROM A CYCLOHEXENE STREAM
silica gel
US 2526499 Refining heavy oils
Col. 2 lines 13+
It has now been discovered that peroxides can be substantially completely removed from higher boiling fractions of petroleum by contacting them with a
bleaching earth such as Attapulgus clay, Floridin, fuller's earth, Olmstead clay, etc., at temperatures between 60' and 120' F., preferably between 70
and 90 F.
US 2058250 Treatment and packaging of ether
http://www.chemistry.ohio-state.edu/ehs/peroxide.htm
From Organic Solvents:
Ethers form peroxides under normal storage conditions. Unless a test shows peroxides to be absent, ethers should not be evaporated or distilled to
near dryness. The rate of formation of peroxides in a given ether depends on the storage conditions. Peroxide formation is accelerated by heat, light
and air. A small amount of moisture will accelerate peroxide formation in most ethers. Ethers kept in the laboratory should be in a dark bottle in an
atmosphere of nitrogen in contact with iron filings or copper powder. Storage in a refrigerator is further recommended.
Peroxide formation in isopropyl ether is rapid. It is advisable to test for peroxide formation, even though it had been freed of them only a short
time before.
Unstabilized isopropyl ether readily forms peroxides and may detonate upon shaking. Isopropyl ether can be stabilized by .001% w of dihydric phenols
such as pyrocatechol, resorcinol or hydroquinone. Commercial isopropyl ether is usually stabalized with para benzylamimophenol. Peroxides can be
destroyed with sulfite solution. Storage in steel containers inhibits the formation of peroxides. Further information on the subject of peroxides in
isopropyl ether can be found in J Chem Eng Data, 5, 383 (1960). The preparation of isopropyl ether using ascarite clay catalyst was published in Zh
Obshch Khim 19, 348 (1949); CA 44 1006 (1950)
[Edited on 26-4-2009 by Vogelzang]
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Sandmeyer
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How? The ipso carbon is quaternary...
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