Esters of Chlorosulfonic Acid<sup>1</sup>

Binkley, W. W.; Degering, Ed. F.

doi:10.1021/ja01278a501

Cited by 18 publications

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“…T h e chlorosulfates were prepared by a modification of the method described by Bi~llcley (24). Sulfuryl chloride (1 mole) was placed in a three-necked flask equipped with a gas inlet tube, a dropping funnel, and a drying tube.…”

Section: E X P E R I M E N T a L Preparatio~t Of Ciriorosulfatesmentioning

confidence: 99%

Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

Buncel¹,

Millington²

1965

Can. J. Chem.

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The solvolysis of the series of alkyl chlorosulfates, ROSO2C1, where R = methyl, ethyl, n-propyl, isobutyl, and ~leopentyl, has been studied in 10 M aqueous dioxane. The relatlve reactivities fit well a solvolytic mechanism involving displacenlent by water on carbon, with OSO2CI a s the leaving group. The change in mechanism of solvolysis from bimolecular with the straight-chain chlorosulfates to unimolecular with neopentyl chlorosulfate is shown by the absence of the lyate ion effect and the observation of rearrangement in the latter case.The entropies of activatio~l in chlorosulfate solvolysis appear to be abnormally large. I t isproposed that the abnormal AF indicates a transition state in which both carbon-oxygen and sulfur-chlorine bond weakening occurs. I t is shown that some other solvolytic reactions that are characterized by abnormally high entropies of activation may be interpreted on the basis of multiple bond fission (fragmentation). The mechanism of Sxi reactions is considered in this context.T h e preceding paper (1) considered in detail the reaction of a typical primary alkyl chlorosulfate with nucleophiles. I-Iere we report the results of a solvolytic study on the series of primary alkyl chlorosulfates ROS02C1, where R is methyl, ethyl, n-propyl, isobutyl, and neopent~l.T h e products of reaction of dilute solutions (0.01 M) of the alkyl chlorosulfates in 10 M aqueous dioxane were determined (Table V, Experimental section). The ionic products are I-12S04 and HCI, forined in quantitative yield. The major organic product in each case was the alcohol, xith a trace of olefin as side product. The major reaction is therefore that represented by eq. [I], i.e. a simple hydrolysis, the olefin being formed most probably by a minor competing elimination reaction. In the case of neopentyl chlorosulfate, the alcohol formed is t h a t from rearrangement, viz. t-pentyl alcohol. PI ROSOICI + 21120 + ROH + H2SOa + HCI.T h e kinetic data were measured in 10 M aqueous dioxane, 85.3% dioxane -14.7% water, by weight. The concentration of chlorosulfate employed \vas 0.01 M. Rates were measured co~~ductimetrically. The half-lives of the hydrolyses were found t o vary from the order of a minute in the case of the methyl coil~pound t o several hours for the neopentyl. The pseudo-first-order rate constants were calculated from usual plots which were linear over a t least 75% of reaction and usually over 90% of reaction. Results for hydrolysis a t several temperatures are given in Table I. Rate constants when calculated for each point individually within a run agreed t o f 1% (standard deviation). The reproducibilitjr between runs was generally also f170. The rate constants given in Table I are the values from two separate runs. E, and log A were obtained from a least-square plot. The error in E, is estimated as &0.35 kcal/mole, and in AS*, k l . O entropy units ( e .~. ) . The Bimoleczilar and the Unimoleczilar MechanismOne of the criteria used in evaluating the mechanism of solvolysis is the lyate ion 'Part 11 in...

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Section: E X P E R I M E N T a L Preparatio~t Of Ciriorosulfatesmentioning

confidence: 99%

Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

Buncel¹,

Millington²

1965

Can. J. Chem.

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“…EXPERIMENTAL illaterials it-PropyI chloros~llfate was prepared after the method of Binkley (15). Dioxane, analytical reagent grade, was purified by refluxing over sodium for 24 h, followed by fractional distillation.…”

Section: Added Reagent ( M O L E S I L X I$)mentioning

confidence: 99%

SOLVOLYSIS OF ALKYL CHLOROSULFATES: PART I. REACTION OF n-PROPYL CHLOROSULFATE WITH NUCLEOPHILES

Buncel¹,

Millington²

1965

Can. J. Chem.

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The effect of various reagents on the rate of hydrolysis of n-propyl chlorosulfate in 10 aqueous dioxane is reported. I-Ialide ions increase the rate of reaction (I-> Br-> C1-) but perchlorate is without effect. Hydroxide and pyrrolidine have a strong accelerating effect, but only a t higher concentrations. These observations sopport a bimolecular mechanism: rate-determining displace~nex~t by nucleophile on carbon, with OSO2C1-as the leaving group. The present results are not In accord with a previous proposal that alkyl chlorosulfates react by rate-determining sulfur-chlorine bond fission followed by fast displacelnent by nucleophile on carbon.Alkyl chlorosulfates,~ ROS02C1, conzprise a class of acyl halide which has been only slightly studied in the past, in comparison with, for example, the structurally related chlorosulfites, ROSOCl, or the sulfonyl chlorides, RSO2Cl. I t is only recently that the diverse reactions of chlorosulfates have been utilized in organic synthesis, by Jones and co-workers (I) of this laboratory in the field of carbohydrate chemistry. The complexity of these reactions have pointed t o the necessity of detailed studies of relatively simple compounds and it is with this purpose that this series of studies was initiated. The present paper reports the results of perhaps the simplest and most basic study, that of aqueous hydrolysis of a typical primary alkyl chlorosulfate.Early studies (2) of the hydrolysis of methyl chlorosulfate in water ascribed three concurrent modes of reaction to the ester, to give the hydrogen sulfate, chloride, and inethanol (eqs.[I]-[3]); in addition some dimethyl ether xvas often observed. These reactions were heterogeneous, due to insolubility of the chlorosulfates in water.More recently Hall (3) found that under honlogenous conditions, in a nledium of aqueous dioxane, reaction occurred only according t o eq. [3]. Hall also carried out the first kinetic study on this class of acyl halide and compared their reactivity with the related sulfonyl chlorides and sulfa~nyl chlorides. I-Ie studied methyl and ethyl chlorosulfates and came t o certain conclusions concerning their nlechanism of reaction. However, these conclusions needed a reevaluation in view of the recent work by Jones et al. (1). In the present work, carried out in 10 ilJ aqueous dioxane, the effect of a variety of reagents has been investigated to ascertain the intimate nature of the hydrolysis. RESULTS Rate 01 Neutral HydrolysisThe products of reaction of a 0.01 M solution of n-propyl chlorosulfate in 10 1 1 l aqueous dioxane were first examined. The ionic products are HtSO? and HC1, formed in

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“…Methyl chlorosulfonate was prepared from freshly distilled sulfuryl chloride and dry methanol essentially according to the method of Binkley and Degering (8) in 48% yield: bp 55-56 OC (39 mm); n25D 1.4112 1-Hexene and l-octene, stored over commercial sulfate, were distilled shortly before use.…”

Section: Methodsmentioning

confidence: 99%

One-step synthesis of esters of aliphatic .beta.-chloro sulfonic acids. Their sequential conversion to other sulfonic acid derivatives

Heller¹,

Lorah²,

Cox³

1983

J. Chem. Eng. Data

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CH?c c , E ( e V ) < 4 b 5 4b0 E B i n d i n g E n e r g y B i n d i n g E n e r g y Flgure 4. X-ray photoelectron spectrum of I I I f : (a) N(ls) energy region, (b) C(1s) energy region. a pressure of less than lo-* torr. Samples were mounted on aluminum mesh at room temperature. ( a ) Reaction of Arylhydrazone -N -carboxylic Esters ( I ) and Hydrazlne Hydrate. A mixture of the hydrazone ester (0.01 mol) and the hydrazine hydrate (0.01 mol) in 50 mL of ethanol was refluxed on a water bath for a period of 5 h. Evaporation of the solvent left a viscous oil, which proved to be the arylhydrazone (I I). Crystallization of I I a from petroleum ether (60-80 "C) gave pale yellow crystals, mp 62 " C . The other hydrazones gave oily materials. ( b ) Reactlon of Arythydrazones ( I I a -g ) and Hydrochloric AcM. A mixture of the arylhydrazone (0.01 mol) in ethanol (20 mL) and 6 N HCI (5 mL) was warmed on a water bath for 5 min. A heavy solid was precipitated, which was filtered off and crystallized from ethanol to give azines of thiophene-2carboxaldehyde (I IIa), furan-2-carboxaldehyde (I1 Ib), pyrrole-2carboxaldehyde (I I IC), 5-methylthiophene-2-carboxaldehyde ( I 1 Id), indole-3-carboxaldehyde (I I Ie), N-methylpyrrole-2carboxaldehyde (I I If), and pyridine-4-carboxaldehyde (I I Ig).Azine I I I a was also prepared by refluxing an alcoholic solution of the arylhydrazone-N-carboxylic ester Ia and aqueous sodium hydroxide (10%) for 1 h. The alcohol was evaporated, and the product was crystallized from petroleum ether (60-80 "C) to give a product, which proved to be identical with IIa. This product was treated with hydrochloric acid, as mentioned above, to yield azine IIIa.( c ) Preparation of Authentlc Samples.(1) Hydrazone I I a was prepared by refluxing equimolecular amounts of thiophene-2-carboxaldehyde and hydrazine hydrate in ethanol for a period of 5 h and then worked up as described previously. (2) Azines IIIa-g were prepared by refluxing the corresponding heterocyclic aldehyde (2 mol) and hydrazine hydrate (1 mol) in ethanol and then worked up. The products proved to be identical with those obtained from procedure b.Elemental analyses were performed and submitted for review. Reglstry No. la,A one-step synthesis of methyl 2thiorohexane-1-and 2-chlorooctane-1-sulfonate by the novel free-radical addition of methyl chlorosulfonate to 1-hexene and 1-octene, respectively, Is reported. These products were converted by standard techniques into the corresponding sodium and benzylthiuronlum P-chiorosulfonlc acid salts and sulfonyl chlorides. Dehydrochlorination of these latter products with triethylamine afforded reglospecific formation of trans-a,p-unsaturated sulfonyl chlorides, which were transformed by conventional methods into sodium and benzylthiuronlum unsaturated and saturated sulfonlc acid salts. Eleven new compositions of matter are reported. Seven l-phenyl-2-[2-( 6-substituted qulnolyl)]ethanoneswere synthesized by the condensatlon of 2methyl-6-substkuted qulnollnes and methyl benzoate wlth sodlum hydrlde as the con...

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Esters of Chlorosulfonic Acid¹

Cited by 18 publications

References 0 publications

Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

SOLVOLYSIS OF ALKYL CHLOROSULFATES: PART I. REACTION OF n-PROPYL CHLOROSULFATE WITH NUCLEOPHILES

One-step synthesis of esters of aliphatic .beta.-chloro sulfonic acids. Their sequential conversion to other sulfonic acid derivatives

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Esters of Chlorosulfonic Acid1

Cited by 18 publications

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Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

Hydrolysis of a Series of Primary Alkyl Chlorosulfates: Entropy of Activation as a Criterion of Fragmentation in Solvolytic Reactions

SOLVOLYSIS OF ALKYL CHLOROSULFATES: PART I. REACTION OF n-PROPYL CHLOROSULFATE WITH NUCLEOPHILES

One-step synthesis of esters of aliphatic .beta.-chloro sulfonic acids. Their sequential conversion to other sulfonic acid derivatives

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Esters of Chlorosulfonic Acid¹