Q Alcohols

The propylene-based chemicals, n- and isobutanol and 2-ethyl-1-hexanol [104-76-7] (2-EH) dominate the product spectmm. These chemicals represent 71% of the world s total oxo chemical capacity. In much of the developed world, plasticizers (qv), long based on 2-EH, are more often and more frequendy higher molecular weight, less volatile Cg, and C q alcohols such as isononyl alcohol, from dimerized normal butenes isodecanol, from propylene trimer and 2-propyl-1-heptanol, from / -butenes and aldol addition. Because of the competition from the higher molecular weight plasticizer alcohols,... 

DiisononylPhthalate andDiisodeeylPhthalate. These primary plasticizers are produced by esterification of 0x0 alcohols of carbon chain length nine and ten. The 0x0 alcohols are produced through the carbonylation of alkenes (olefins). The carbonylation process (eq. 3) adds a carbon unit to an alkene chain by reaction with carbon monoxide and hydrogen with heat, pressure, and catalyst. In this way a Cg alkene is carbonylated to yield a alcohol a alkene is carbonylated to produce a C q alcohol. Due to the distribution of the C=C double bond ia the alkene and the varyiag effectiveness of certain catalysts, the position of the added carbon atom can vary and an isomer distribution is generally created ia such a reaction the nature of this distribution depends on the reaction conditions. Consequendy these alcohols are termed iso-alcohols and the subsequent phthalates iso-phthalates, an unfortunate designation ia view of possible confusion with esters of isophthaUc acid. 

Trimelhtate Esters. These materials are produced by the esterification of a range of alcohols with trimeUitic anhydride (TMA), which is similar ia stmcture to phthaHc anhydride with the exception of the third functionaHty (COOH) on the aromatic ring. Consequendy, esters are produced ia the ratio of three moles of alcohol to one mole of anhydride. Common esters ia this family are tris-2-ethyhexyl trimeUitate (trioctyl trimeUitate, TOTM) L79TM, an ester of mixed semilinear C and C alcohols and L810TM, an ester of mixed linear Cg and C q alcohols. 

Define or identify each of the following terms (a) organic chemistry, (b) total bond order, (c) condensed formula, (d) structural formula, (e) fine formula, (/) hydrocarbon, (g) alkane, (h) aUcene, (/) alkyne, j) aromatic hydrocarbon, (k) saturated, (1) delocalized double bond, (m) isomerism, (n) cycloalkane, (o) radical, (p) functional group, (q) alcohol, (r) ether, (s) aldehyde, (f) ketone, (u) carbonyl group, and (v) ester. 

Oct-l-ene Nonanal (31), nonan-l-ol (23), branched Q-alde-hydes (5), branched Q-alcohols (2) RUj(CO)i2... 

Both ethanol and lactic acid, products of anaerobic respiration, accumulate in the pea seed prior to the penetration of the radicle through the enclosing testa [38, 39]. Following radicle emergence their levels diminish as they are metabolized under the conditions of increasing aerobiosis. This event is accompanied by increased oxygen uptake, CO2 output and a fall in R.Q. Alcohol... 

Trimellitate plasticisers are very low volatility plasticisers with reasonable low temperature properties and efficiency. As esters of C7 to C q alcohols and trimellitic anhydride, they find their main application in high temperature electrical cables, although their exceptionally low volatility also makes them useful for anti-fogging automobile leathercloth. They have largely taken over from di-pen-taerythritol esters due to their better processing characteristics and better hydrolytic stability. 

Figure 1 compares data reduction using the modified UNIQUAC equation with that using the original UNIQUAC equation. The data are those of Boublikova and Lu (1969) for ethanol and n-octane. The dashed line indicates results obtained with the original equation (q = q for ethanol) and the continuous line shows results obtained with the modified equation. The original equation predicts a liquid-liquid miscibility gap, contrary to experiment. The modified UNIQUAC equation, however, represents the alcohol/n-octane system with good accuracy. 

Monoethanolainine, 2-aminoethyl alcohol, 2-hydroxyelhy amine, HOCH2CH2NH2. M.p. 10-5°Q b.p. 17UC. 

Place I ml. of benzyl alcohol in a boiling-tube and add 6 ml. of 10% sodium hydroxide solution add also 6 ml. of water to moderate the subsequent reaction, otherwise the rise in temperature may cause hydrolysis of some of the ester produced. Now add r-q g. of finely powdered />-nitrobenzoyl chloride, and shake the well-corked tube vigorously. The mixture becomes warm, and the solid ester rapidly... 

The first report of oxidative carbonylation is the reaction of alkenes with CO in benzene in the presence of PdCh to afford the /3-chloroacyl chloride 224[12,206]. The oxidative carbonylation of alkene in alcohol gives the q, f3-unsaturated ester 225 and /3-alkoxy ester 226 by monocarbonylation, and succinate 111 by dicarbonylation depending on the reaction conditions[207-209]. The scope of the reaction has been studied[210]. Succinate formation takes... 

Simple esters cannot be allylated with allyl acetates, but the Schiff base 109 derived from o -amino acid esters such as glycine or alanine is allylated with allyl acetate. In this way. the o-allyl-a-amino acid 110 can be prepared after hydrolysis[34]. The Q-allyl-o-aminophosphonate 112 is prepared by allylation of the Schiff base 111 of diethyl aminomethylphosphonates. [35,36]. Asymmetric synthesis in this reaction using the (+ )-A, jV-dicyclohex-ylsulfamoylisobornyl alcohol ester of glycine and DIOP as a chiral ligand achieved 99% ec[72]. 

Compounds other than a-halocarbonyls and thiourea can lead to 2-aminothiazoles. Thus 3-halogenoalkynes (120) condensed with thiourea in absolute alcohol give 2-aminothiazoles (Scheme 56a) (497), with Rj = Me, Et, n-Bu, H CPh, and HjCCgH tR-p R2 = H, Ph, CgH4R, and Q-naphthyl. Yields ranged from 20 to 80% (497). 

Propargyl alcohol is a primary skin irritant and a severe eye irritant and is toxic by all means of ingestion all necessary precautions must be taken to avoid contact with Hquid or vapors. The LD q is 0.07 mL/kg for white rats and 0.06 mL/kg for guinea pigs. 

Linear paraffins in the C q to range are used for the production of alcohols and plasticizers and biodegradable detergents of the linear alkylbenzene sulfonate and nonionic types (see Alcohols Plasticizers Surfactants). Here the UOP Molex process is used to extract / -paraffins from a hydrotreated kerosine (6—8). 

The olefin product contains 1.1% of residual / -paraffins. Essentially similar results have been obtained in commercial operations on Cg—C q and C g feedstocks. The desorbents used are generally hydrocarbon mixtures of lower boiling range than the feed components. The concentrated olefin stream may then be used for production of detergent alcohols. 

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

Toxicity studies on trifluoroethanol show acute oral LD q, 240 mg/kg acute dermal LD q, 1680 mg/kg and acute inhalation L(ct) Q, 4600 ppmh. Long-term subchronic inhalation exposure to 50—150 ppm of the alcohol has caused testicular depression in male rats, but no effects were noted at the 10 ppm level (32). Although the significance of the latter observations for human safety is unknown, it is recommended that continuous exposure to greater than 5 ppm or skin contact with it be avoided. 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

Rya.nia., The root and stem of the plant yania speciosa family Flacourtiaceae, native to South America, contain from 0.16—0.2% of iasecticidal components, the most important of which is the alkaloid ryanodine [15662-33-9] C25H250 N (8) (mp 219—220°C). This compound is effective as both a contact and a stomach poison. Ryanodine is soluble ia water, methyl alcohol, and most organic solvents but not ia petroleum oils. It is more stable to the action of air and light than pyrethmm or rotenone and has considerable residual action. Ryania has an oral LD q to the rat of 750 mg/kg. The material has shown considerable promise ia the control of the European com borer and codling moth and is used as a wettable powder of ground stems or as a methanohc extract. Ryanodine uncouples the ATP—ADP actomyosia cycle of striated muscle. 

Pyrethroid Esters of Benzene Acetate. These insecticides have more extensive stmctural optimization in both acid and alcohol moieties. Fenvalerate [51630-58-17, a-cyano-(3-phenoxyphenyl)methyl (+)-(2R,5)"Ct"isoprop5i-4-chlorophenylacetate (24) d 1.17, vp 1.4 p.Pa at 25°C), a mixture of four isomers, is soluble in water to 0.3 mg/L The rat oral LD q is 450 mg/kg. Esfenvalerate [66230-04-4] is the (+)-2-(i, 5)-isomer (mp 59°C). The rat LD qS are 75, 458 (oral), and the rabbit dermal LD q is 2000 mg/kg. These pyrethroids are widely used general-purpose insecticides for field, vegetable, and fmit crops. 

Diesters have been produced primarily by esterification of a C -branched-chain alcohol with adipic (C ), a2elaic (C ), or sebacic (C q) diacid. Di(2-ethylhexyl)sebacate [122-62-3] was quite generally used in military greases and MIL-L-7808 jet engine oil, but more recent demands and price competition have led to use of a variety of diesters. 

Acute oral LD q data for nitro alcohols in mice are given in Table 1. Because of their low volatiHty, the nitro alcohols present no vapor inhalation ha2ard. They are nonirritating to the skin and, except for 2-nitro-1-butanol, are nonirritating when introduced as a 1 wt % aqueous solution in the eye of a rabbit. When 0.1 mL of 1 wt % commercial-grade 2-nitro-1-butanol in water is introduced into the eyes of rabbits, severe and permanent corneal scarring results. This anomalous behavior may be caused by the presence of a nitro-olefin impurity in the unpurifted commercial product. 

DiaLkyl peroxides may be prepared by reaction of alcohols or alkyl trifluoromethanesulfonates with organomineral peroxides of siUcon, tin, and germanium (44,108), where Q = Sn and Ge ... 

DiaIkyl or diaryl dithiophosphoric acids are obtained readily from alcoholysis of phosphoms(V) sulfide. Thus, P4S q reacts with ethyl alcohol as follows ... 

Reactivity is affected by particle size. Smaller particles react faster. However, the dominant factor for reactivity is the soHdification rate. Material that is soHdified quicker reacts faster with alcohol (30). Commercial P4S q is a soHd solution containing P4S2Q, P4SC), P4Sy, free sulfur, etc (33). SoHdification rate... 

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