Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Reexamination Certificate
2002-03-11
2003-12-30
Solola, Taofiq (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
C549S554000, C549S563000
Reexamination Certificate
active
06670474
ABSTRACT:
BACKGROUND OF THE INVENTION
The epoxy intermediates and resins industry (Encyclopedia of Chemical Technology, Volume 9. Fourth Edition. John Wiley & Sons Page 730) is a multibillion dollar business that is based on the following technology that involves no less than ten chemical reactions. This application is a continuation-in-part of Ser. No. 60/284,325 filed Apr. 17, 2001.
Benzene+propylene→isopropylbenzene
Isopropylbenzene→cumene hydroperoxide
Cumene hydroperoxide→phenol+acetone.
Phenol+acetone→“Bis-A” or Phenol+formaldehyde→“Bis-F”
Propylene+chlorine→allyl chloride
Allyl chloride+sodium hydroxide+chlorine→propylene chlorohydrins
Propylene chlorohydrins+sodium hydroxide→epichlorohydrin
Bis-A+epichlorohydrin+NaOH→“Bis-A glycidol ether”
Bis-A glycidol ether+Bis-A→epoxy resin
Sodium chloride+water→chlorine+sodium hydroxide.
Several aspects of the above reaction sequence have negative process implications with regards to yields, chlorinated byproducts, hydraulic load and biological hazards. These include but are not limited to the following: (a) benzene is a known carcinogen, (b) Bis-A is an endocrine disrupter (mimics estrogen), (c) chlorination of propylene to allyl chloride (step 5) and the addition of hypochlorous acid (step 6) yield higher chlorinated byproducts resulting in ~⅓ pounds of chlorinated waste per pound of epichlorohydrin. In addition, the process requires a chlor-alkali facility, hence a local source of salt and huge volumes of water. The products and processes of the present invention ameliorate if not eliminate some of the disadvantages of prior art epoxy products and processes.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to the preparation of bis-esters and ethers of allylarylphenols and the epoxidation of the allyl moiety to provide novel bis-epoxide ester and ether intermediates useful in the preparation of epoxy resins. The epoxy ethers and esters of carboxylic, carbonic, phosphoric and sulfonic acids of the present invention are represented by the following formulas:
where Y is a CO, CO
2
or SO
2
, AR is a divalent unsubstituted or substituted aromatic, halogen-substituted aromatic or cyano-substituted aromatic hydrocarbon radical having from 6 to 20 carbon atoms, Z is a divalent hydrocarbon or ether radical having from 1 to 20 carbon atoms, including YZY being CO, and R* is an alkyl, aryl, arylalkyl, alkoxy, aryloxy or arylalkoxy radical having from 0-20 carbon atoms.
Preferred aromatic “AR” radicals include divalent benzene, naphthalene, toluene, chlorobenzene, cyanobenzene, xylene and ethylbenzene radicals. Preferred hydrocarbon “Z” radicals include divalent aliphatic radicals such as divalent methane, ethane, butane, and cyclohexane, divalent aromatic radicals such as divalent benzene, toluene, xylene and ethylbenzene radicals. Preferred ether “Z” radicals include such divalent radicals as divalent ethoxyethane, ethoxypropane, propoxypropane, butoxyethane methoxybenzene, and ethoxybenzene. Preferred R* radicals include methyl, ethyl, propyl, isobutyl, cyclohexyl, phenyl, benzyl, naphthyl, toluyl and xylyl.
DETAILED DESCRIPTION OF THE INVENTION
The preparation of allylarylphenols used in the present invention is well documented in the chemical literature and is illustrated for 2-allylphenol. The formation of the ether and the rearrangement are carried out in the same reactor.
C
6
H
5
OH+CH
2
═CHCH
2
X+base→C
6
H
5
OCH
2
CH═CH
2
+HX,
where X is Cl, Br, acetate, tosylate, or similar leaving group.
C
6
H
5
OCH
2
CH═CH
2
+H
+
→2-CH
2
═CHCH
2
C
6
H
4
OH
The preparation of bis-aromatic disulfonyl chlorides is also well-documented in the literature and is achieved via the sulfonation or chlorosulfonation of aromatic compounds (“Friedel Crafts and Related Reactions”, Volume 3, Part 2, page 1355, Interscience Publishers, 1964, C. M. Suter, “Organic Chemistry of Sulfur Compounds”, Chapter 3 John Wiley and Sons, 1944, and “Organic Functional Group Preparations”, S. R. Sandler and W. Karo, Academic Press 1968, page 506). The reactions are preferably carried out in 1,2-dichloroethane as solvent. If higher reaction temperatures are required for the bis sulfonation, the reaction may be performed without a solvent. Reaction of the aromatic disulfonyl chloride with two equivalents of the allylarylphenol in the presence of an acid acceptor gives the desired bis-sulfonate ester which is converted to the desired bis-epoxide in essentially quantitative yield with standard utilized oxidants e.g., peracetic acid, 3-chloroperbenzoic acid, hydrogen peroxide, t-butyl hydroperoxide etc. The latter two reagents require a metal catalyst (“Oxidations in Organic Chemistry”, M. Hudlicky, ACS Monograph 186, page 60. American Chemical Society).
The allylarylphenyl ester of dicarboxylic acids are conveniently prepared from the reaction of the dicarboxylic acid dichloride with the allylarylphenol in an inert solvent such as toluene, dichloromethane, 1,2-dichloromethane etc. in the presence of a hydrogen acceptor such as pyridine, triethylamine, etc. The use of the hydrogen acceptor can be eliminated by simply refluxing the phenol and acid chloride in a higher boiling solvent to effect displacement of the anhydrous HCl that may be recovered for alternate uses. If a lower dialkyl ester of the dicarboxylic acid is available, ester exchange of the allylarylphenol in the presence of a transesterification catalyst can serve as an alternative route to the bis-aryl ester (“Encyclopedia of Chemical Technology”, Volume 9. Fourth Edition, John Wiley & Sons, page 755, “Survey of Synthesis”, Calvin Buehler and D. E Pearson, Wiley Interscience 1970, page 101 and “Preparation of Esters using Polyphosphate Ester”, J. H. Adams, J. G. Paul and J. R. Lewis, Synthesis, 429-30, 1979). The oxidation methods are identical as described above for the sulfate esters.
In the manner described for the preparation of allylphenyl esters from dicarboxylic acid dichlorides, the allylphenyl esters of dicarbonic acids are prepared from the corresponding bis-chloroformates with two equivalents of allylphenol. Similarly a carbonic acid ester, is prepared from two equivalents of allylphenol and phosgene.
The allylaryl esters of the phosphoric and phosphonic acids are readily prepared from the acid dichlorides since phosphorus oxychloride, POCl
3
, is the basic phosphorus precursor (“Organophosphorus Compounds”, G. M. Kosolapoff, John Wiley, 1950). Thus, utilization of an inert solvent and an acid acceptor as described above for the carboxylic acids gives high yields of the desired allylaryl esters that are then oxidized to the bis-epoxides as described above.
The allylaryl ethers are prepared by displacement reactions of the desired dichloride with either the allylaryl phenoxide anion or displacement by the 2,3-epoxypropylphenoxide anion. For substrates that require higher temperatures to carry out the displacement such as 4-chlorophenyl sulfone, the preferred anion is the 2,3-epoxypropylphenoxide. With the allylaryl phenoxide, displacement occurs but the 2,3-olefinic bond undergoes thermal isomerization to the 1,2-olefin. With the more reactive olefins, such as 1,4-dichlorobutane and 3,6-dichloropyridazine, olefin isomerization is not a problem. For unreactive aryl halides, reaction conditions for the Ullman reaction ether synthesis is required. Within the scope of the present invention, optimum reaction conditions can be obtained in a routine manner.
The following are examples of allylarylphenols that may be reacted with either derivatives of organic acids or dihalo compounds to form the compounds of this invention: 2-allylphenol, 2-allyl-6-methylphenol, 4-allyl-2,6-dimethylphenol, 2-allyl-4-dodecylphenol, 2-allyl-4-methoxyphenol, 2-allyl-4-phenoxyphenol, 2-allyl-4-cyclohexylphenol, 3-allyl-4-hydroxy ethyl benzoate, 2-allyl-4-chlorophenol, 2-allyl-4-cyanophenol, 2-allyl-4-benzylphenol, 2-allyl-4-chloromethylphenol, 1
Sandt Bernd W.
Solola Taofiq
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