2- Chloro-l-butanol

For alcohols, EHOMO decreases as the number of chlorines increases. The dataset is l-chloro-2-propanol 2,2/2-trichloro-l/l-ethanediol 2,2,2-trichloro-ethanol 2,2-dichloroethanol 2-chloroethanol 3-chloro-l,2-propanediol 3-chloropropanol and 4-chloro-l-butanol. HOMO represents 94.4% of the variance in the linear regression equation therefore, the probability of getting a correlation of -0.9721 for a sample size of eight is less than 1% (see Figure 5.17). 

CHLORO-l-BUTANOL see CEU500 CHLOROBUTIN see CD0500 CHLOROBUTINE see CD0500 N-(3-CHLORO-l-sec-BUTYLACETONYL)-p-TOLUENESULFONAMIDE see THH470... 

Because the resolution with acylase gave a theoretical maximum yield of only 50% and required separation of the desired product from the unreacted enantiomer at the end of the reaction, we next tried to prepare the amino acid by reductive amination of the corresponding ketoacid, a process with a theoretical maximum yield of 100%. A variety of ketoacids can be converted to L-amino acids by treatment with ammonia, reduced nicotinamide adenine dinucleotide (NADH), and a suitable amino acid dehydrogenase. 2-Keto-6-hydroxyhexanoic acid (in equilibrium with its cyclic hemiketal form) was prepared by chemical synthesis starting from 4-chloro-l-butanol, which was... 

Chlorobutyl acetate and 4-chloro-l-butanol Acetyl chloride (65 g), tetrahydrofuran (50 g b.p. 66°), and ZnCl2 (0.01 g) are boiled for 90 min under reflux with exclusion of moisture, whereafter distillation gives 76% of 4-chlorobutyl acetate, b.p. 78-79°/15 mm, 90-91°/20 mm. Yields are considerably less if no ZnCl2 or more ZnCl2 or A1C13 is added.1038 Transesterification with methanol and a little concentrated HC1 or p-toluenesulfonic acid gives 80% of 4-chloro-l-butanol, b.p. 64-65°/3 mm in this reaction a temperature of 40°, finally 50°, should not be exceeded, otherwise tetrahydrofuran is re-formed. 

Chloro-l-butanol is obtained more simply by leading HC1 into boiling tetrahydrofuran until the temperature of the boiling mixture reaches 103.5-105.5° (ca. 5 h). The product is... 

These reagents are prepared by the reaction of 4-chloro-l-butanol with paraformaldehyde and hydrogen bromide or hydrogen chloride in about 50% yield. 

When 4-chloro-l-butanol is treated with a strong base such as sodium hydride, NaH, tetrahydrofuran is produced. Suggest a mechanism. 

The hydroxyl group and halide end up on the same molecule because of the cyclic nature of the ether. When a cyclic ether is cleaved, it cleaves to one molecule, not two. 4-chloro-l-butanol can continue to react with HCl to produce the desired product, 1,4-dichlorobutane, as indicated ... 

Structure and functional group Cl—CH2 —CH2—CH2—CH2—OH, exhibits reactivity of primary alcohol and alkyl halides Synonyms 4-chloro-l-butanol 4-chlorobutyl alcohol... 

The parent member of this class of compounds, l,3-dioxepan-2-one (169) has been synthesized either by treating 4-chloro-l-butanol with ammonium bicarbonate in acetonitrile under a CO2 atmosphere <80MIP479522> or by reaction of butylene oxide and solid CO2 in the presence of MnBr2 <72JAP47026786> (Equation (25)), and (169) has b n used as a solvent for the halogenation of ketene <73GEP(0)2247764>. 

General base catalysis was first proposed for the cyclization of 4-chloro-1-butanol on the basis of a Br0nsted plot involving the reactions catalyzed by water, hydroxide ion, borate ion, and water. The three-point Br0nsted plot of the 4-chloro-l-butanol studies yielded a slope of 0.25, which was interpreted as implying that the transfer of the alcoholic proton is about 25 % complete at the transition state. " Solvent isotope effects of Hio/ DiO = 1-28 and koo / oh = 107 were measured and interpreted as... 

Table 13. Rates of Hydrolysis of 4-Chloro-l-butanol at 50°C in Aqueous Media ...

Determination of the chlorine isotope effects for the base-catalyzed cyclization of 2-chloroethanol and 4-chloro-l-butanol (see Table 13) have provided support for the conclusions drawn from solvent isotope effects that is, carbon-chlorine bond rupture in 2-chloroethanol is greater than that in 4-chloro-l-butanol at the transition state (i.e., compare entries in the first and second columns of Table 14). Following a similar line of reasoning in the analysis of the chlorine isotope data of the hydroxide- and water-catalyzed cyclizations (i.e., compare entries in the second and third columns of Table 14) requires the conclusion that there is more carbon-chlorine... 

Chloro-l-butanol and hydroxide each initially 0.03-0.08M. Average of five to seven runs R > 99 %. 

Measurements of the temperature coefficient of activation/ the volume of activation/ and the entropy of activation have also been reported for the cyclization of 4-chloro-l-butanol. While there are some differences of opinion as to the interpretation of these values/ support of the kinetic evidence of a weakly anchimerically assisted process is indicated. 

A majority of the remaining solvolytic studies involve base catalysis, and 0 is probably the reactive oxygen species present. 0 -5 participation was suggested to account for the formation of the bicyclic ether (192) from the alkaline hydrolysis of trans-4-chlorocyclohexanol. The rate of reaction is 1100 times less than that of 4-chloro-l-butanol under the same conditions, but, as discussed above, O attack was not suggested in the hydrolysis of the latter. 

Anchimeric assistance by the hydroxyl group has been reported in some more unusual substrates than those above, e.g., bisethylenediaminecobalt (111) complexes. In aqueous hydroxide solution (217) reacts some 50 times faster than 4-chloro-l-butanol to form the cyclic chelate (218). The experimental observations support the mechanism shown. In this system HO-5 competes with N-3 participation. An analysis of equilibria and rate constants indicated that lysis of bromide by the coordinated nitrogen to produce the aziridine (219) is 10 -10 times faster than by the coordinated oxygen. 

The cyclic ether tetrahydrofuran (THE) can be synthesized by treating 4-chloro-l-butanol with aqueous sodium hydroxide (see below). Propose a mechanism for this reaction. 

STRATEGY AND ANSWER Removal of a proton from the hydroxyl group of 4-chloro-l-butanol gives an alkox-ide ion that can then react with itself in an intramolecular Sn2 reaction to form a ring. 

Treatment of 4-chloro-l-butanol, C1CH2CH2CH2CH20H, with NaOH in DMF solvent leads to rapid formation of a compound with the molecular formula C4H8O. Propose a structure for this product and suggest a mechanism for its formation. 

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