Preparation 7-Toluenesulfonyl chloride, reaction

Dichlorotoluene (l,3-dichloro-2-methylben2ene) is prepared from the Sandmeyer reaction on 2-arnino-6-chlorotoluene. Other methods include ring chlorination of -toluenesulfonyl chloride followed by desulfonylation (81), and chlorination and dealkylation of 4-/ f2 -butyltoluene (82) or... 

Tetrachlorotoluene, C H Cl (mol wt 229.93) (1,2,3,5-tetrachloro-4-methylben2ene), is prepared from the Sandmeyer reaction on 3-arnino-2,4,6-trichlorotoluene. 2,3,4,5-Tetrachlorotoluene (l,2,3,4-tetrachloro-5-methylben2ene) is the principal isomer in the further chlorination of 2,4,5-trichlorotoluene. Exhaustive chlorination of -toluenesulfonyl chloride, followed by hydrolysis to remove the sulfonic acid group yields... 

Deoxy-D-jcylo hexose 6-(dihydrogen phosphate) (21) has also been synthesized (2) the reaction sequence makes use of 3-deoxy l 2,5 6-di-O-isopropylidene D-galactofuranose (16), a compound that can be easily prepared from D-glucose (2, 60). The mono-isopropylidene derivative (17) formed by partial hydrolysis of the di-ketal is converted into the 6-tosylate (18) by reaction with one molar equivalent of p-toluenesulfonyl chloride. From this the epoxide (19) is formed by reaction with sodium methoxide. Treatment of the anhydro sugar with an aqueous solution of disodium hydrogen phosphate (26) leads to the 6-phosphate (20)... 

Transformations to polymer-bound amino compounds, which are often useful as ligands for metals ions or other free species (67), employ a wide selection of organic reactions. Quaternary ammonium salts result from heating isolated polymer tosylate with tertiary amine they may also be prepared in one step from (hydroxyethyl)polystyrene and toluenesulfonyl chloride and a two-fold excess of amine. 

This procedure for the preparation of l-ethyl-3-(3-dimethyl-amino)propylcarbodiimide and its salts is a modification of one that has been published.4 Unsymmetrical carbodiimides have also been prepared by desulfurization of the corresponding thioureas with mercuric oxide3 or by dehydration of the corresponding ureas with -toluenesulfonyl chloride in pyridine.4 Unsymmetrical 1,3-disubstituted ureas are best prepared by the reaction... 

For the preparation of N- 2-(methoxyphenyl)cthyl ]-4-mcthylbcn-zenesulfonamide (1) from Ameba resins A and Ba-Bd, 100 mg (0.089 mmol) Ameba resin A was added to a glass peptide reaction vessel, suspended in 3.0 mL 1,2-dichloroethane (DCE note 2), and treated with 26 pL (0.18 mmol, 2.0 Eq.) 2-(4-methoxy-phenyl)ethylamine (note 2) and 38 mg (0.178 mmol, 2.0 Eq.) sodium triacetoxyborohydride (note 2). The suspension was shaken for 1 h treated with 5 mL MeOH filtered on a glass frit and washed with DCM (2x5 mL), DMF (2x5 mL), MeOH (2 x 5 mL), and DCM (2x5 mL). The resin was dried under vacuum (0.5 torr) at room temperature overnight. The resin was suspended in 1.5 mL DCM, treated with 155 pL (0.89 mmol, 10.0 Eq.) N,N-diisopropylethylamine (note 2) and 85 mg (0.445 mmol, 5.0 Eq.) p-toluenesulfonyl chloride (note 2), and shaken for 3.5 h. The reaction mixture was filtered on a glass frit, washed with DCM (2 x 5 mL), DMF (2x5 mL), MeOH (2x5 mL), and DCM (2 x 5 mL), and dried under vacuum (0.5 torr) at room temperature for 2h. The resin was treated with 2.5 mL of a solution of 5% trifluoroacetic acid (note 2) in DCM, shaken for 15 min, filtered on a glass frit, and washed with DCM (3x5 mL). The combined filtrate and washings were concentrated and dried under vacuum (0.5 torr) at room temperature overnight to afford 18.0 mg (66%) N- [2-(methoxyphenyl)ethyl] -4-methylbenzenesulfonamide (1). 

Dialkyl N-(benzoxazin-4-yl)methylenemalonates and their optically active forms (1728) were prepared in the reaction of the appropriate pheny-laminomethylenemalonate (1727), triphenylphosphine, and diethyl azodi-carboxylate in THF at -20°C (89EUP3228I5). The hydroxyl group of racemic and optically active phenylaminomethylenemalonates (1727) were tosylated with p-toluenesulfonyl chloride in pyridine, and the products were cyclized by heating in DMF at 80°C in the presence of potassium carbonate and a catalytic amount of 18-crown-6-ether to give 1728 (89EUP322815). 

Section 7.8). Other classes of derivatives are thus most conveniently prepared from the sulfonyl chloride. Reaction with an alcohol leads to formation of a sulfonate ester. Two common sulfonyl chloride reagents employed to make sulfonate esters from alcohols arep-toluenesulfonyl chloride, known as tosyl chloride, and methanesulfonyl chloride, known as mesyl chloride (see Section 6.1.4). Note the nomenclature tosyl and mesyl for these groups, which may be abbreviated to Ts and Ms respectively. 

Apart from the reaction of diazomethane with benzoyl chloride,5-6 diazoacetophenone has been prepared by the reaction of 2-aminoacetophenone hydrochloride with sodium nitrite,7 from the mixed anhydride of benzoic acid and ethyl carbonate with diazomethane,8 from benzoyl chloride and potassium methyldiazotate,9 by treating the enamine formed from 2-formylacetophenone and N-methylaniline with p-toluenesulfonyl azide,10 and from the reaction of the sodium enolate of 2-formylacetophenone with p-toluenesulfonyl azide.11... 

Despite the immediate application of unimolar sulfonylation for the preparation of many w-sulfonic esters of sugar derivatives, a kinetic study of the reaction was not made until 1942 Hockett and Downing136 then found that, with p-toluenesulfonyl chloride-pyridine at 23° 2°, the time to half-esterification for a mole of l,2 3,4-di-0-isopropylidene-D-galactose (with a primary hydroxyl group) is 0.272 hours (see Fig. 2), whereas for l,2 5,6-di-0-isopropylidene-D-glucose (with a secondary hydroxyl group) it is 20.2 hours (see Fig. 3). That is, after about 120 minutes, nearly all of the compound with the free primary hydroxyl group... 

Small Quantities. Wear eye protection, laboratory coat, and nitrile rubber gloves. Work in the fume hood. Add 60 mL of 2.5 M sodium hydroxide (prepared by carefully dissolving 6 g of NaOH in 60 mL of cold water) to a 100-mL, three-necked, round-bottom flask equipped with a stirrer and thermometer, placed on a steam bath. The p-toluenesulfonyl chloride (0.05 mol, 9.5 g) is added in small portions. If the reaction is sluggish (no dissolution or rise in temperature), heat the mixture to about 90°C. When the initially added material has dissolved, add the remainder in small portions. After the addition is complete, continue heating until a clear solution is obtained. Cool the mixture to room temperature, neutralize with dilute hydrochloric or sulfuric acid, and then wash into the drain.3... 

To a solution of (S)-0-p-toluenesulfonyl-3-butyn-2-ol (11.2 g, 50.0 mmol), prepared by addition of p-toluenesulfonyl chloride and triethylamine to (S)-3-butyn-2-ol, in methanol (100 ml), was added 55% aqueous hydroxylamine (30 ml, 0.50 mol) and the reaction mixture was stirred at room temperature for 40 h. The reaction mixture was cooled to 10°C and concentrated HCI (50 ml) was added dropwise. The reaction mixture was concentrated in vacuum and the residue was partitioned between H20 (50 ml) and ethyl acetate (200 ml). The 2-phase mixture was cooled to 10°C and taken to pH 8 with 50% aqueous NaOH solution (60 ml). After stirring for 15 min the layers were separated and the aqueous phase was extracted twice with 200 ml of ethyl acetate. The combined ethyl acetate extracts were cooled to 10°C and a solution of KOCN (8.1 g, 0.10 mmol) in H20 (30 ml) was added, followed by dropwise addition of 11 ml of concentrated HCI, and the reaction mixture was... 

O-Methylcaprolactim has been prepared by the reaction of cyclohexanone oxime, p-toluenesulfonyl chloride, and methanol 3 and by the procedure described above, which is a modification of the method given in the patent literature.4... 

For an example of a related cyclisation reaction using caesium carbonate as a base in DMF, see Protocol 3. The starting ditoluenesulfonamide (m.p. 119-20°C) is readily prepared by reaction of the corresponding diamine with p-toluenesulfonyl chloride (aq NaOH/Et2OI. 

Ring closure of acylamines prepared from ethylenediamine also yields imidazoles,88 but this reaction will be discussed in Section II, E as formation of the 1 2- and 2 3-bonds. When 2,2 -dipyridyl compounds react with methylene iodide,84 bromine in pyridine, or p-toluenesulfonyl chloride in pyridine,85 imidazolium salts are produced. 

Lx)ng-chain fatty acid cellulose esters were synthesized by the acid-chloride-pyridine reaction with different degrees of substitution. Hydrolyzed soybean oil was used as an unsaturated fatty acid [82]. The preparation of cellulose esters with substituted benzoic acids in the presence of p-toluenesulfonyl chloride in pyridine was investigated [83]. The substituents included NO2, Cl, Me, and MeO. The substituent and its position (ortho, meta, or para) did not influence the reaction significantly. 

Symmetrical aliphatic ethers (C -Ci,) are prepared by the removal of water from alcohols under acidic conditions. Thus, in the preparation of diisoamyl ether, the alcohol is heated with concentrated sulfuric acid or p-toluenesulfonyl chloride in a flask equipp>ed with a condenser and a water sep>arator. The top layer of alcohol and ether is returned to the reaction flask until water no longer separates. Any alcohol remaining in the ether is converted to the higher-boiling triisoamyl borate, and the ether is purified by fractional distillation. Several suitable water separators have been described. High reaction temperatures must be avoided to prevent the formation of unsaturated hydrocarbons (cf. method 19). 

RC = CCH,X — RCX = C==CH,. /S.y- and 7,S-Acetylenic alcohols can be transformed to the halides in better yields by an alternative procedure, which consists in their esterification with p-toluenesulfonyl chloride and subsequent cleavage of the ester by the action of sodium iodide, lithium chloride, or calcium bromide in an appropriate solvent (60-90%). Halo ethers are prepared by the action of phosphorus tribromide on hydroxy ethers, as in the preparation of /3-ethoxyethyl bromide (66%). In a similar manner, /3-halo esters have been prepared without appreciable dehydration of the /3-hydroxy ester (40-60%). The reaction of cyanohydrins leads to a-halo nitriles. Treatment of 2-nitro-l-propanol with phosphorus pentachloride gives l-chloro-2-nitropropane (47%). ... 

A. l-Ethyl-3-(3-dimetkylamino)propylcarbodiimide. A solution of 100 g. (1.41 moles) of ethyl isocyanate (Note 1) in 750 ml. of methylene chloride is prepared in a 5-1. three-necked flask equipped with a meehanical stirrer, an immersion thermometer, and a 500-ml., pressure-equalizing, addition funnel (Note 2). The flask and its contents are cooled to 5° in an ice bath, and a solution of 144 g. (1.41 moles) of N,N-dimethyl-l,3-propanedi-amine in 250 ml. of methylene chloride is added through the addition funnel at a rate such that the reaction temperature does not exceed 10° (Note 3). On completion of this addition 500 ml. of triethylamine is added to the flask, and a solution of 300 g. (1.6 moles) of -toluenesulfonyl chloride in 300 ml. of methylene chloride is placed in the addition funnel and added to the reaction... 

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