Secondary thionyl chloride

The acid function of an aliphatic chain bonded to a thiazole ring can be esterified. The corresponding acid chloride can also be prepared by the action of thionyl chloride, though the reaction is often accompanied by secondary reactions and gives poor yields (49, 74). 

Because tertiary alcohols are so readily converted to chlorides with hydrogen chloride, thionyl chloride is used mainly to prepare primary and secondary alkyl chlorides. Reactions with thionyl chloride are nonrrally carried out in the presence of potassium carbonate or the weak organic base pyridine. 

Reaction of dibenzylamine with ethylene oxide affords the amino alcohol, 82. Treatment of that product with thionyl chloride gives the a-sympathetic blocking agent, dibenamine (83). (Condensation of phenol with propylene chlorohydrin (84) gives the alcohol, 85. Reaction with thionyl chloride affords the chloride (86). Use of the halide to alkylate ethanolamine affords the secondary amine (87). Alkylation of this last with benzyl chloride... 

Condensation of normeperidine (81) with 3-chloropropan-l-ol affords the compound possessing the alcohol side chain (88). The hydroxyl is then converted to chlorine by means of thionyl chloride (89) displacement of the halogen by aniline yields pimino-dine (90). ° Condensation of the secondary amine, 81, with styrene oxide affords the alcohol, 91 removal of the benzyllic hydroxyl group by hydrogenolysis leads to pheneridlne (92). ... 

Phenylacetonitrile is alkylated with secondary butyl bromide and the resultant nitrile is hydrolyzed to 3-methyl-2-phenylvaleric acid. The acid is converted to the acid chioride with thionyl chloride and the acid chloride is in turn reacted with 1-methyl-4-piperidinol. Finally dimethyl sulfate is reacted with the ester. 

Primary and secondary alcohols are best converted into alkyl halides by treatment with either thionyl chloride (SOCl2) or phosphorus tribromicle (PB ). These reactions, which normally take place readily under mild conditions, are less acidic and less likely to cause acid-catalyzed rearrangements than the HX method. 

The simplest method of nitrile preparation is the Sj 2 reaction of CN with a primary or secondary alkyl halide, as discussed in Section 20.5. Another method for preparing nitriles is by dehydration of a primary amide, RCONH2. Thionyl chloride is often used for the reaction, although other dehydrating agents such as POCI3 also work. 

E—Lithium Lithium anode Iodine, sulfur dioxide, thionyl chloride, and iron disulfide Secondary Lithium-iron disulfide batteries, lithium-ion batteries, and lithium polymer batteries... 

The synthesis of 1,3-selenazoles from A -phenylimidoyl isoselenocyanates has been reported. N-phenylimidoyl isoselenocyanates 94 are prepared from N-phenylbenzamides 92. Treatment of 92 with thionyl chloride affords N-phenylbenzimidoyl chlorides 93, which yield imidoyl isoselenocyanates 94 on reaction with potassium isoselenocyanate. The imidoyl isoselenocyanates 94 were transformed into selenoureas 95 with either ammonia or primary or secondary amines. Reaction of 95 with an activated bromomethylene compound such as bromoacetophenone in the prescence of a base gave the 1,3-selenazole 97 via the salt 96 <00HCA1576>. 

Thionyl chloride (SOCI2) has often been used as a dehydrating agent for primary, secondary, as well as tertiary p-hydroxy amides. With primary hydroxyl amides, the intermediate p-chloro amide can usually be isolated, which will then... 

Wuts and co-workers recently reported that the Vilsmeier reagent is superior to thionyl chloride for the cyclodehydration of primary and secondary p-hydroxy amides to prepare oxazolines, in particular, for oxazoline 18b, which is used in Taxol synthesis (Scheme 8.10). Some other examples are shown in Table 8.5 (Fig. 8.3). As expected, inversion of configuration at the alcohol bearing carbon atom is observed. Of the examples examined, serine afforded low yields due to the formation of dehydroalanine. The reaction is conveniently carried out in pyridine at room temperature. p-Chloro amides are also formed, which can be converted to the oxazoline with DBU, generally using the same mixture without isolation. The... 

The reaction of primary or secondary alcohols with thionyl chloride is a general method far preparing the corresponding chlaro compounds. In the first step a chlorosulfue ROSOG is formed from which S02 is eliminated in a relatively slow step. This decomposition is... 

The propargyl alcohols react with trivalent phosphorus halides to give allenic phosphorus esters as described in Scheme 3 and Table VI. In the case of aryl-substituted alkynols or highly hindered t-propargyl alcohols which contain no free acetylenic —H, thionyl halides or phosphorus trihalides yield bromo- or chloroallenes [74d], Thionyl chloride also reacts in a similar fashion with a wide variety of unhindered secondary alcohols (structure XV) to give a mixture of the chloroallene and chloroalkyne [74a-d]. 

Gerrard [11] had shown earlier that the slow addition of 0.5 mole of thionyl chloride to a mixture of pyridine (1.0 mole) and hydroxy compounds (n-butyl, M-amyl, or ethyl lactate—0.1 mole) gives pyridine hydrochloride and good yields of the sulfite (see Eq. 4). Primary and secondary alcohols with an aromatic nucleus in the a-position give chlorides in the absence of catalysts [12], For example, diphenylmethanol gives the chloride even at —78°C. Sulfites derived from tertiary alcohols are not known. The further addition of thionyl chloride converted the sulfite to the chlorosulfinate (see Eq. 5 and Table I). 

Konovalova and Orekhov103 demonstrated that the primary hydroxyl group in platynecine is more reactive to acylation than the secondary. For example, use of more or less drastic conditions yields platynecine di- or mono-benzoate, respectively. Pyrrolizidine alcohols can be esterified with inorganic acids e.g., mild treatment of platynecine with thionyl chloride yields the cyclic sulfite ester hydrochloride79 (see Section III, A). 

Hydroxymethylpyridazines are easily oxidized with selenium dioxide to the corresponding aldehydes. Oxidation of the corresponding secondary alcohols with chromic acid in aqueous sulfuric acid gives ketones, while oxidation of a hydroxymethyl group with permanganate leads to the pyridazinecarboxylic acids. Hydroxymethyl groups are converted into chloromethyl groups with thionyl chloride or phosphorus oxychloride. 

The reaction of primary or secondary alcohols with thionyl chloride is a general method for preparing the corresponding chloro compounds. In the first step a chlorosulfne ROSOC) is formed from which S02 is eliminated in a relatively slow step. This decomposition is facilitated by a tertiary amine, e.g. pyridine. The ammonium salt RO-SON+.Cl— formed from the chlorosulftte is subsequently attacked on carbon (in R) by CF. Since nucleophilic substitutions on propargylic carbon proceed more easily than on carbon in saturated compounds, it may be expected that the conversion of propargylic chlorosulfites into the chlorides will take place under relatively mild conditions. 

Indeed, a nearly parabolic dependence of surface film growth in exposure time was found for lithium and calcium in thionyl chloride solutions [33,34], In any event, the above description is only a first approximation. In reality, the films are not necessarily homogeneous, and, as described in the previous section, water contamination may play an important role, and possible dissolution-deposition cycles of the surface species, as well as their possible secondary reactions with solution species, may considerably distort the above parabolic dependence of / (film) versus t. 

---