- N-Nitroso Sultams: On the Direction of Approach of Nucleophiles to the Sulfonyl Group
-
The N-nitroso derivatives of propanesultam, butanesultam, and pentanesultam were synthesized along with N-nitropropanesultam and N-nitro-N-methylmethanesulfonamide.The decompositions of the N-nitroso sultams, wich increase in rate with increasing ring size, yield the corresponding sultones and also varying amounts of regenerated sultams.These reactions are discussed in terms of higher energy pathway involving approach of the nucleophile in a direction between of sulfonyl oxygens (on the O, O, N face) and a lower energy pathway involving the conformer which permits approach of the nucleophile trans to and colinear with one of the coordinate covalent oxygen atoms (on R, O, N face). The mechanisms of the decomposition of the N-nitro sulfonamides and the tosyloxy diimide N-oxides are also discussed.N-nitrosopropanesultam (and the butyl analoque) are potent inhibitors of proteinase α-chymotrypsin.
- White, Emil H.,Lim, Hyung M.
-
-
Read Online
- 1,2-Oxathiolan, a Simple Sultene
-
Evidence is presented which indicates that pyrolysis of N-(3-hydroxypropylthio)phthalimide gives 1,2-oxathiolan as a volatile product via an intermediate tentatively identified as a cyclic oligomer.
- Davis, Anthony P.,Whitham, Gordon H.
-
-
Read Online
- Oxidative Cleavage and Cyclization of Disulfide Carboxylic Acids and Alcohols by Aqueous Iodine: A Facile Route to Five-Membered Ring Sultines
-
The kinetics and mechanism of the oxidative cleavage by aqueous iodine of disulfide carboxylic acids and alcohols are presented.There is evidence for intramolecular interaction of the oxygen nucleophiles.The sole product of the iodine oxidation of 3,3'-dithiodipropanol is the sultine 1,2-oxathiolane 2-oxide, which is formed after the rate-determining step, apparently via rapid cyclization of the sulfenyl iodide.The anchimeric assistance provided by the neighboring carboxylate group in the reaction of 3,3'-dithiodipropanoic acid is responsible for the pH profile of the rate of oxidative cleavage.At a given pH, the rate law for the reaction is -d/dt = kI3->(0.0905->-1 + 0.0019->-2).The inverse second term in iodide ion not has been observed previously in kinetic studies of disulfide reactions and is interpreted as evidence for a disulfide-iodonium complex.
- Doi, Joyce Takahashi,Luehr, Gary W.,Musker, W. Kenneth
-
-
Read Online
- 1,3-propane sultone preparation method
-
The invention relates to a 1,3-propane sultone preparation method, which comprises: S1, completely mixing in a reaction container by using 3-chloropropanol and sodium sulfite as raw materials and using water as a solvent, controlling the temperature at 25-120 DEG C, carrying out a reaction for 4-48 h, carrying out pressure reducing dewatering concentration, adding concentrated hydrochloric acid tothe concentrated liquid, carrying out acidification, controlling the temperature at 0-80 DEG C, stirring for 1-24 h, filtering, and concentrating the filtrate to obtain 3-hydroxypropanesulfonic acid;S2, controlling the temperature of the concentrated liquid obtained in the step S1 at 40-110 DEG C, and carrying out pressure reducing concentrating to carry out dewatering ring closure on the 3-hydroxypropanesulfonic acid in the concentrated liquid to obtain a crude product containing 1,3-propane sultone; and S3, rectifying the crude product containing 1,3-propane sultone to obtain 1,3-propane sultone. According to the present invention, the method has characteristics of short process route, less three-waste and simple post-treatment, wherein the total yield can achieve more than 90%, and the purity of the product can achieve more than 99.9%.
- -
-
Paragraph 0033-0048; 0049
(2019/10/01)
-
- Solvent-free method for preparing 1,3-propane sultone
-
The invention discloses a solvent-free method for preparing 11,3-propane sultone. According to the method, propenol and ammonium sulfite are used as reaction raw materials; and deionized water is adopted as medium. The preparation method comprises the following steps: stirring ammonium sulfate and deionized water; at 20-50 DEG C, preparing a mixed solution from acrolein, an initiator and deionizedwater, dropwise adding the mixed solution into a beaker, and carrying out catalytic reaction to generate an aqueous solution of 3-hydroxypropylammonium sulfonate; adding calcium hydroxide to carry out alkalization reaction, after alkalization is completed, adding concentrated sulfuric acid for acidification treatment to obtain 3-hydroxypropanesulfonic acid and solid calcium sulfate, and performing filtration to obtain an aqueous solution of the 3-hydroxypropanesulfonic acid; carrying out concentration and reduced pressure rectification to obtain a target product; adding a certain amount of calcium hydroxide and water into kettle residues, performing hydrolysis to obtain an aqueous solution of calcium 3-hydroxypropanesulfonate, adding concentrated sulfuric acid for acidification treatment,performing filtration to obtain an aqueous solution of 3-hydroxypropanesulfonic acid, and carrying out concentration and reduced pressure rectification to obtain the target product. The method has the advantages of simple process, simple raw materials, no solvent and no waste, and the yield can reach 95%.
- -
-
Paragraph 0010; 0023-0028
(2019/12/02)
-
- Preparation method of 1,3-propane sultone
-
The invention discloses a preparation method of 1,3-propane sultone. The preparation method of the 1,3-propane sultone comprises the following steps of (1) under the existence of tetraethylammonium bromide, reacting 1,3-dichloropropane and sulfur dioxide in acetonitrile under the action of a constant current so as to obtain 1,3- propane sulfincacid lactone; (2) carrying out oxidation reaction on the prepared 1,3-propane sulfincacid lactone and an oxidizing agent in an organic solvent to obtain the 1,3-propane sultone. The preparation method of the 1,3-propane sultone provided by the inventionhas the advantages of higher yield, high purity, cheap and easy-to-get raw materials, mild reaction conditions, simple preparation process and the like.
- -
-
Paragraph 0032; 0036; 0039
(2018/07/07)
-
- Method for preparing 1,3-propane sultone
-
The invention discloses a method for preparing 1,3-propane sultone. The method comprises the following steps: 1) mixing 1,3-dihalopropane and a sulfonating agent and a solvent, and performing a sulfonation reaction under certain temperature to obtain 1-halogenated-3-sodium 1-propanesulfonate; 2) adding the 1-halogenated-3-sodium 1-propanesulfonate in water, adding strong acid for adjusting a pH value to 1-3, performing acidifying treatment, performing concentration, filtering the material to remove inorganic salt, and performing concentration to a dry state to obtain 1-halogenated-3-moropholino ethanesulfonic acid; and 3) heating the 1-halogenated-3-moropholino ethanesulfonic acid under vacuum condition, and performing a lactonization reaction to obtain the 1,3-propane sultone. The methodhas the advantages that 1) the toxicity of an used raw material 1,3-dihalopropane is smaller, the 1,3-dihalopropane is safer, is easily available, and is recoverable and repeatedly used, and is convenient for storage, so that raw material and operation cost of the raw material can be greatly reduced; and 2) three-waste output in the method is less, environment pollution is reduced, environment pollution is reduced, the purity of the produced product is high and can reach more than 99%, and the water content of the product is lower than 0.1%.
- -
-
Paragraph 0026; 0031; 0034; 0042
(2018/07/30)
-
- A method for preparing 1, 3 - propane lactone (by machine translation)
-
The invention discloses a 1, 3 - propane lactone of the preparation method, comprises the following steps: first preparing a calcium chloride solution, then adding citric acid mixed solution prepared A, and mixed with the sodium polyacrylate solution preparing mixed solution B, then rapidly added to the sodium carbonate solution precipitation, for preparing porous calcium carbonate, and peroxy benzoic acid in the solution is impregnated to obtain the catalyst; the allyl sodium sulfonate and sulfuric acid solution, adding catalyst to react, adding ethanol solution of sodium hydroxide reaction, and finally adding hydrochloric acid, to obtain 3 - hydroxy propane sulfonic acid; the obtained 3 - hydroxy propane sulfonic acid and hexane mixed in added to the three-mouth flask, stirring the reaction, after the reaction cooled to the room temperature, vacuum distillation, to obtain the target product 1, 3 - propane lactone. The method is simple in operation, low energy consumption, high product yield. (by machine translation)
- -
-
Paragraph 0026; 0033; 0034; 0041; 0042; 0049; 0050; 0057
(2019/01/08)
-
- Preparation method of 1, 3-propane sultone
-
The invention discloses a preparation method of 1, 3-propane sultone. The preparation method comprises the following steps: (1), in the presence of an amine compound and an initiator, performing a free radical addition reaction on allyl alcohol and bisulfite in water to produce 3-hydroxypropanesulfonate, and acidifying to obtain 3-hydroxypropanesulfonic acid; (2), then performing a cyclization reaction on the 3-hydroxypropanesulfonic acid at the vacuum degree of 0-10mmHg and the temperature of 150-200 DEG C to produce the 1, 3-propane sultone. By the preparation method, the environment pollution can be reduced, so that the environment friendliness is better; in addition, the preparation method has the advantages of simple and safe operation, relatively ideal yield and the like.
- -
-
Paragraph 0030; 0035; 0037-0042
(2018/07/30)
-
- Method for preparing 1,3-propane sultone
-
The invention discloses a method for preparing 1,3-propane sultone. The method includes the steps that (1) 1,3-propanesulfonic acid is prepared: sodium sulfite, sodium bisulfite and allyl alcohol are added into a reactor under the room temperature condition, a pH value is regulated to be 5 to 5.5, infrared radiation induction is adopted, azo diisobutyl nitrile performs catalytic reaction for 2 to 3 hours, concentrated hydrochloric acid is added, the reaction is performed at the temperature of 85 to 90 DEG C for 2 to 3 hours, generated salt is removed through filtration, and n-butyl alcohol is added into filtrate to perform extraction separation so as to obtain the 3-hydroxy-1-propanesulfonic acid; (2) the 1,3-propane sultone is prepared: pyridinium p-toluenesulfonate and zeolites are added, dehydration reaction is performed at the temperature of 50-60 DEG C for 2-3 hours, distillation is performed to obtain 147-149 DEG C of fraction, and calcium oxide is added to perform heating reflux for 1-2 hours to obtain the 1,3-propane sultone. The product prepared by means of the method is high in yield and purity. In addition, the moisture content of the product is mostly above 0.1%, the amplification effect and other problems do not exist, and the method is suitable for industrial production.
- -
-
Paragraph 0039; 0040; 0042
(2016/10/07)
-
- 1. 3 - propane sulfonic acid lactone preparation method (by machine translation)
-
The invention discloses 1, 3 - propane sultone preparation method, steps are as follows: (1) to the catalyst and sodium bisulfite as raw materials, deionized water as the medium, in the initiator catalytic addition react to generate the 3 - hydroxy c sodium sulfonate; (2) adding sulfuric acid to the reaction solution in the acidification, then distilled to remove the excessive water, adding anhydrous ethanol extraction and filtration, to obtain 3 - hydroxy propane sulfonic acid ethanol solution; (3) the 3 - hydroxy propane sulfonic acid ethanol solution of the first normal pressure distillation to remove the ethanol, and get the 1, 3 - propane sulfonic acid lactone; (4) is added to the distillation still in the sodium hydroxide aqueous solution to perform hydrolysis, then adding sulfuric acid acidified, then adding anhydrous ethanol extraction and filtration, to obtain 3 - hydroxy propane sulfonic acid ethanol solution, then remove ethanol from atmospheric distillation, and get the 1, 3 - propane sulfonic acid lactone. The above preparation method can reduce the reaction temperature, and the product of the molar yield high, fixed less waste, easily to obtain high-purity product. (by machine translation)
- -
-
Paragraph 0021; 0022; 0023; 0024; 0025; 0026
(2017/06/02)
-
- Initiators of addition of sodium hydrogen sulfite to allyl alcohol
-
Synthesis of a versatile sulfoalkylating agent, 1,3-propanesultone, was studied.
- Baranovskaya
-
p. 2047 - 2048
(2007/10/03)
-
- Formation and opening of 1,3-propanesultone ring
-
New procedure of 1,3-propanesultone synthesis by dehydration of 3-hydroxypropane-1-sulfonic acid is developed to improve the yield of the final product. Conditions of 1,3-propanesultone ring opening under the action of water during extraction are studied. 1996 MAEe cyrillic signK Hayκa/Interperiodica Publishing.
- Baranovskaya
-
-
- HYDROXYALKANESULFONYL CHLORIDES FROM CHLORINATION OF HYDROXYALKANESULFINATE SALTS IN A NONPOLAR MEDIUM: 3-HYDROXY-1-PROPANESULFONYL AND 4-HYDROXY-1-PROPANESULFONYL AND 4-HYDROXY-1-BUTANESULFONYL CHLORIDES
-
3-Hydroxy-1-propanesulfonyl chloride (1b) was obtained for the first time (admixed with 10percent of propane sultone, 2b) by chlorination of a dichloromethane suspension of sodium 3-hydroxy-1-propanesulfinate 93b). 4-Hydroxy-1-butanesulfonyl chloride (1c) containing 13percent butane sultone (2c) was prepared similarly from 3c.The cyclizations of 1b and 1c in CDCl3 containing 1-butanol (0.9 M) showed first order rate constants of 1.4 x 10-4 and 6.4 x 10-5 s-1, corresponding to effective concentrations of 4.5 x 102 and 2.1 x 102 M, respectively.Reaction of triethylamine in ethanol-d (a) with 1b gave exclusively the undeuterated sultone (2b), evidently by a direct cyclization, and (b) with 1c produced mainly ethyl 4-hydroxy-1-butanesulfonate largely monodeuterated at the α-position, and presumably formed by way of the sulfene (6c).
- King, J. F.,Rathore, Rajendra
-
p. 165 - 172
(2007/10/02)
-
- Organic sulfur mechanisms. 24. Preparation and reaction of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride
-
2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqeous solution of 2-mercaptoethanol (4a) with chlorine.This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride.Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nucleophilic ring opening to form the products.In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14), the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxyl group to give the ethenesulfonate derivatives (13 or 22).Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b).A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxonium ion (27) is discussed.
- King, James Frederick,Hillhouse, John Henry
-
p. 1583 - 1593
(2007/10/02)
-
