Phenols octylphenols

Caswell No. 513D EINECS 248-310-7 EPA Pesticide Chemical Code 064118 Octyl phenol Octylphenol tert-Octylphenol Phenol, (1,1,3,3-tetramethylbutyl)- Phenol, octyl- (1,1,3,3-Tetramethylbutyl)phenol USAF RH-6. Mixture of 0, m and p-isomers. 

For monosubstituted alkylphenols, the position of the alkyl radical relative to the hydroxyl function is designated either with a numerical locant or ortho, meta, or para. The alkyl side chain typically retains a trivial name. Thus 4-(l,l,3,3-tetramethylbutyl)phenol, 4-/ f2 octylphenol, and para-tert-octy Tph.eno (PTOP) all refer to stmcture (1). 

Di- and Triisobutylcncs. Diisobutylene [18923-87-0] and tnisobutylenes are prepared by heating the sulfuric acid extract of isobutylene from a separation process to about 90°C. A 90% yield containing 80% dimers and 20% trimers results. Use centers on the dimer, CgH, a mixture of 2,4,4-trimethylpentene-1 and -2. Most of the dimer-trimer mixture is added to the gasoline pool as an octane improver. The balance is used for alkylation of phenols to yield octylphenol, which in turn is ethoxylated or condensed with formaldehyde. The water-soluble ethoxylated phenols are used as surface-active agents in textiles, paints, caulks, and sealants (see Alkylphenols). 

A few synthetic substituted phenols are also used in the manufacture of oil-soluble resins. They include p-tert-butylphenol, / -tert-amylphenol, p-tert-octylphenol, /7-phenylphenol and dihydroxyphenylpropane (bis-phenol A). 

Tetralin vapor, 17 76 Tetralkyl pyrophosphates, 19 27 4-(l,l,3,3-Tetramethylbutyl)phenol. See 4-tert-Octylphenol... 

High resolution (HR)-GC chromatograms of NP show a complicated isomer profile [46] with several tens of peaks (see Fig. 2.1.5(b), top). In contrast, commercial standards of OP are usually made up from f-octylphenol [p-(l,l,3,3-tetramethylbutyl)phenol], which is essentially... 

For commercial octylphenol products the synthesis is usually performed with the starting material 1,1,3,3-tetramethylbutane, thus resulting in t-OPs with only a single major compound for each possible ortho, meta (minor), or para-substituted) phenyl positional isomer. High-resolution chromatograms of OPs are therefore much less complicated than those of NPs (compare Fig. 2.1.4(a)-(c)), although the presence of 11 minor constituents in parai t-octylj-phenol has been reported [126]. 

Xie, Z Le Calve, S Feigenbrugel, V., Preup, T.G., Vinken, R., Ebinghaus, R., and Ruck, W. Henry s law constants measurements of nonylphenol isomer 4(3, 5-dimethyl-3-heptyl)phenol, fertia/y-octylphenol and y-hexachlorocyclohexane between 278 and 298 K, Atmos. Environ., 38(29) 4859-4868, 2004. 

Alkylphenol Ethoxylates (APE). The hydrophobes of most commercial APE are made by reacting phenol with either propylene trimer or diisobutylene to form nonylphenol or octylphenol. These products contain an aromatic moiety and extensive branching in their alkyl chains. It has been shown that APE biodegrade more slowly and less extensively than LPAE (3.15-20). The difference is more pronounced when the treatment system is operating under stress conditions such as low temperatures and high surfactant loadings. 

The first reactions concerned (Simons and Archer, 27) alkylation of benzene with propylene to form isopropylbenzene, with isobutene to form f-butylbenzene and di-f-butylbenzene, and trimethylethylene to form amylbenzene. Later on (Simons and Archer, 28) studied these and other reactions in more detail and showed that high yields could be obtained and that the product was not contaminated with tars or other obnoxious impurities. It was shown that the products obtained with trimethylethylene were mono- and di-f-amylbenzene, that phenyl-pentane resulted from the use of pentene-2, and that cyclohexene produced cyclohexylbenzene. Cinnamic acid reacted with benzene (Simons and Archer, 29) to form /3-phenylpropionic acid and allyl benzene reacted with benzene to form 1,2-diphenylpropane. It is interesting to note that although allyl alcohol reacted with benzene to form 1,2-diphenylpropane, the intermediate in the reaction, allylbenzene, was isolated and identified. This shows that in this case the hydroxyl reacted at a more rapid rate than the double bond. Both di- and triisobutylene reacted with phenol (Simons and Archer, 30) at 0°, when using hydrogen fluoride containing only relatively small quantities of water, to form f-butyl-benzene, but diisobutylene with 70% hydrogen fluoride produced p-f-octylphenol. Cyclohexene reacted with toluene to form cyclohexyl-toluene and octene-1 rapidly reacted with toluene to form 2-octyltoluene (Simons and Basler, 31). 

La Guardia MJ, Hale RC, Harvey E, et al. 2000. Endocrine disruptors (octylphenol, nonylphenol, nonyl phenol ethoxylates and polybrominated diphenyl ethers) in land applied sewage sludge biosolids. In Preprints of extended abstracts. American Chemical Society, Division of Envrionmental Chemistry. 

Phenolic compounds are used in commercial or consumer products or building materials (Rudel et al., 2001), especially ethoxylated alkylphenols of octylphenol and nonylphenol, which are widely used in surfactants (Ying, Williams and Kookana, 2002). They are known as endocrine disrupting compounds (EDC) as they bear hormonally active properties. Other EDCs found indoors include phthal-ates (Section 11.2.7), certain pesticides, organotin compounds (Section 11.2.5) and polybrominated diphenyl ethers (Section 11.2.8) (Rudel et al., 2001, 2003). 

Rudel et al. (2001) reported concentrations of nonylphenol and its mono- and di-ethoxylates up to 14 mg kg 1 in house dust for a 7-sample pilot study in the USA. Concentrations of ethoxylated octylphenols did not exceed 5 mg kg"1. Of the more than 30 phenols analyzed only 4-nonylphenol was found in air with concentrations up to 0.118pgm"3. Wilson, Chuang and Lyu (2001) reported the nonylphenol content of dust samples from 10 child care centers (USA) to be 4.16-13. Smgkg 1 the Bisphenol A content to be 1.04—4.51 mgkg 1, respectively. In their study concentrations in air amounted to 0.052-0.527 ggm 3 for nonylphenol and up to 0.0018ggm 3 for Bisphenol A. 

Results for endocrine disrupting phenols in house dust as reported by Rudel et al. (2003) and Butte et al. (2001) are compiled in Table 11.1. Rudel et al. (2003) sampled indoor air in 120 homes as well. They analyzed both house dust and air for 89 organic chemicals identified as EDCs. The most abundant compounds in air included 4-nonylphenol and 4-t-butylphenol with typical concentrations in the range of 0.050-1.500ggm 3. Saito, Onuki and Seto (2004) collected air samples from houses, offices, and outdoor points. 4-t-butylphenol, 4-t-octylphenol and 4-nonylphenol were detected in both indoor and outdoor air. Concentrations and detection frequencies were higher in indoor air than outdoor air. The maximum levels of 4-t-butylphenol, 4-t-octylphenol and 4-nonylphenol in indoor air were 0.387, 0.0457 and 0.680 ggm 3, respectively. 4-t-butylphenol and 4-nonylphenol were detected with high frequencies (more than 97%) in the indoor air samples. Wilson, Chuang and Lyu (2001) reported a mean of 0.0007 gg m"3 Bisphenol A in the air of 10 child care centers and a mean of 0.203 gg m 3 for the sum of nonylphenol and its ethoxylates. 

Alkylphenol. Alkylphenol is a common surfactant intermediate used to produce alkylphenol ethoxylates. Phenol reacts with an olefin thermally without a catalyst but with relatively poor yields. Catalysts for the reaction include sulfuric acid p-toluene sulfonic acid (PTSA), strong acid resins, and boron trifluoride (BF3). Of these, strong acid resins and BF3 are mostly widely used for the production of surfactant-grade alkylphenols. The most common alkylphenols are octylphenol, nonylphenol, and dodecylphe-nol. Mono nonylphenol (MNP) is by far the most common hydrophobe. It is produced by the alkylation of phenol with nonene under acid conditions. All commercially produced MNP is made with nonene based on propylene trimer. Because of the skeletal rearrangements that occur during propylene oligomerization, MNP is a complex mixture of branched isomers. 

Concerns over their potential to function as endocrine disruptors led to a Japanese study on the levels of alkylphenols in 60 rubber products. Such compounds are used as starting materials in the manufacture of a number of mbber additives, particularly oligomeric phenolic antioxidants. The work concentrated on four compounds p-/er/.butyl phenol (PTBP), p-/er/.octylphenol... 

Alkylphenols (APs), particularly nonylphenols (NPs) and to a lesser extent octylphenols (OPs), are extensively used for the production of alkylphenol polyethoxylates (NPEOs), a class of non-ionic surfactants that has been largely employed for more than 40 years in textile and paper processing and in the manufacture of paints, coatings, pesticides, industrial detergents, cosmetics and spermicidal preparations, as well as various cleaning products. NPs are also used in the manufacturing processes of many plastics and as monomers in the production of phenol/formaldehyde resins. Smaller quantities of NPs are employed in the production of tri(4-nonylphenyl) phosphite as an anti-oxidant for rubber and in the manufacture of lubricating oil additives. 

Mainly POE p-nony I phenol, p-octylphenol, or p-dodecylphenol (sometimes, dinon-ylphenol), derived from disobutylene, propylene trimer, or propylene tetramer. 

During the thirties many substituted phenols were screened for applicability in varnishes. Patents on the preparation of oil-soluble resins were issued to Honel (20) using p-tert-butylphenol and p-tert-amyIphenol and to Turkington and Butler (21) using p-tert-buty Iphenol, octylphenol, and others. Turkington and Allen (22) reported the effect of the alkyl substituent on the phenol and the Influence on resin and varnish properties. Of some 40 tested, only the acid-catalyzed, nonheat-reactive resins made with p-phenylphenol and a few para tertiary alkylated phenols gave good performance. 

Tyloxapol, 4-11,1,3,3-Teiramethytbutyl)phenol polymer with formaldehyde and oxirane oxyethylated tertiary octylphenol formaldehyde polymer oxyethylated tertiary octyl phenol-poly methylene polymer p-isooctylpolyoxyeth-y ten e phenol formaldehyde polymer tyloxypal Aleva ire Superinone Triton A-20 Triton WR-1339. Nonionic detergent with surface-ten si on-reducing properties. Prepn Bock, Rainey, U.S. pat. 2.454,541 (1948 to Rohm Haas) Cornforth et at.. Nature 168, 150 (19SI). 

Beilstein Handbook Reference) A13-10011 BRN 0513992 EINECS 205-426-2 HSDB 5411 NSC 5427 p-Octylphenol 4-t-Octylphenol 4-t-Octylphenol p-terc.Oktylfenol para-t-Octylphenol Phenol, 4-(1,1,3,3-tetramethylbutyl)-. 

EINECS 217-302-5 HSDB 5857 1-(p-Hydroxyphenyl)-octane Phenol, 4-octyl- Phenol, p-octyl- 4-Octylphenol p-Octylphenol para-Octylphenol. 

The chemistry of certain alkylphenols and that of hindered phenols has been discussed in chapter 6 where tabulated material has included introductory reference to compounds considered at length in the present chapter. Alkylphenols possessing longer alkyl chains which are sometimes mono- but usually multi-branched have achieved special industrial interest notably those with Cg and Cg alkyl groups in the 4-position such as 4-t-nonyl- and 4-t-octylphenol. In addition, 4-t-butylphenol has also attained a considerable level of commercial chemical interest and in recognition of the unique position of these types of compound their chemistry is now detailed. 

Boron tiifluoride-dimethylether (BFj.MejO) has been employed. Thus in a continous process phenol and nonene together with fresh and recovered catalyst were reacted at 80-5°C. Distillation gave nonylphenol and both recovered phenol and catalyst. In a similar way octene afforded octylphenol in 92.5% yield while di-isobutylene gave 94% (ref.4). ... 

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