CN1007979B - 2,2-dioxy 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-one and process for the preparation of its non-toxic salt - Google Patents
2,2-dioxy 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-one and process for the preparation of its non-toxic saltInfo
- Publication number
- CN1007979B CN1007979B CN85106284A CN85106284A CN1007979B CN 1007979 B CN1007979 B CN 1007979B CN 85106284 A CN85106284 A CN 85106284A CN 85106284 A CN85106284 A CN 85106284A CN 1007979 B CN1007979 B CN 1007979B
- Authority
- CN
- China
- Prior art keywords
- alkali
- aceto
- acetamide
- compound
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Dioxy 6-methyl-3, 4-dihydro-1, 2, 3,-oxathiazine-4-keone and non-toxic salts thereof are prepared by that acetoacetamide reacts with an S-O compound of a formula I by alkali. In the formula of FSO-[2]Y(I), Y represents F, Cl,-OSO-[2]F or-OSO-[2]Cl, and preferentially adopts F. Pacticularly, potassium salt is a valuable synthetic sweetener.
Description
2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone is the compound that belongs to following formula.
Because on the nitrogen-atoms acidic hydrogen is arranged, this compound can form salt (with alkali).Because their sweet taste is still very strong in some cases, non-toxic salt (for example sodium, potassium and calcium salt) can be used as sweeting agent in foodstuffs industry, sylvite (" A Saisuofa wood potassium ") (acesulfam k) or abbreviation " A Saisuofa wood " (acesulfam) potassium have special importance.
Many different preparations 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method for 3-Evil thiazine-4-ketone and non-toxic salt thereof all is known.Referring to 1973 the 85th volumes of " applied chemistry " (Angewandte Chemie), 22 phase 965-73 pages or leaves are corresponding to 1973 the 12nd volumes of international version, 11 phase 869-76 pages or leaves.In fact all methods all are with isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester (XSO
2NCO
1X=Cl or F) as starting raw material.Isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester and monomethyl acetylene, acetone, etheric acid, tert-butyl acetoacetate or benzyl allyl ethers reaction (normally polystep reaction) and obtain N-chlorine sulphonyl aceto-acetamide or the cyclisation under the effect of alkali (for example potassium hydroxide methanol solution) of N-fluorine sulphonyl aceto-acetamide obtains 2,2-titanium dioxide-6-methyl-3,4-dihydro-1,2, the corresponding salt of 3-Evil thiazine-4-ketone.If necessary, can obtain free De Evil Buprofezin with general method (with acid) by salt.
The method of another Zhi Bei Evil Buprofezin intermediate N fluorine sulphonyl aceto-acetamide is the partial hydrolysate aminosulfonyl fluorine H from isocyanic acid fluorine sulfonyl ester
2NSO
2(DE-OS2 453 063) that F begins.Aminosulfonyl fluorine (H in this method
2NSO
2F, with the acetoacetyl agent diketene of equimolar amount almost when the inert organic solvents neutralization has amine to exist, reaction between in-30 to 100 ℃, reaction is carried out (with triethylamine as amine) by following equation:
N-fluorine sulphonyl aceto-acetamide
N-fluorine sulphonyl aceto-acetamide is used alkali then, and for example the methanol solution with potassium hydroxide obtains sweeting agent with the general fashion cyclisation:
The A Saisuo magic arts
Though in some cases, 2 of the productive rate that currently known methods obtains feeling quite pleased, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2, (with starting raw material aminosulfonyl halogen is benchmark for 3-Evil thiazine-4-ketone and non-toxic salt thereof, almost up to theoretical amount 85%), but these methods still need to improve, especially industry law, because need to use isocyanic acid chlorine sulfonyl ester or fluorine sulfonyl ester as starting raw material, these very uneasy obtaining.In fact, preparation isocyanic acid chlorine sulfonyl ester and fluorine sulfonyl ester need considerable preventive measures and safety precautions, are quite to bother because starting raw material operates sometimes, particularly HCN and HF.Isocyanic acid chlorine sulfonyl ester and fluorine sulfonyl ester are made according to following formula.
Therefore, except other problem, also advise by aceto-acetamide with at least about the SO of two times of molar weights
3Reaction prepares 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone and non-toxic salt thereof, if suit in the inorganic or organic solvent at inert, and subsequently with alkali neutralization with the formation of acid produce 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone is (the applying for a patent 3410 440.2-HOE B4/F 065) that suits.
N-alkylsulfonyl aceto-acetamide may be earlier by-mole aceto-acetamide and-mole SO in the reaction
3Generate, and then further with-mole SO
3Cyclisation obtains 2,2-titanium dioxide 6-methyl-3, and 4-dihydro-1,2,3-Evil thiazine-4-ketone:
If want to obtain salt, can be 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the 3-thiazine-4-ketone potassium hydroxide that neutralizes-for example use:
So just having obtained is about 30～90% the productive rate of theoretical value of benchmark with the aceto-acetamide.
If aceto-acetamide and SULPHURYL CHLORIDE SO
2Cl
2Reaction rather than and SO
3Reaction obtains α, α-dichlorated product with regard to α-chlorination that aceto-acetamide takes place
CH
3COCCl
2CONH
2, this compound is pressed the following formula fracture with alkali:
CH
3COCCl
2CONH
2+ NaOH → CH
3COONa+Cl
2CHCONH
2Referring to JP-OS 73-39431, with reference to " U.S. chemical abstract " 1973 the 79th volumes 65827a bar digest.
Exceeding is to have found that sulfonic acid fluoride reacts in a completely different way as other special fluoro sulfonyl compounds and aceto-acetamide and alkali unexpectedly, that is generates 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone or its corresponding salt.
Therefore, the present invention relates to by aceto-acetamide and-the S-O compound begins to prepare 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method for 3-Evil thiazine-4-ketone and non-toxic salt thereof, this comprises aceto-acetamide and the reaction of S-O compound when having alkali to exist with following formula I:
FSO
2Y （Ⅰ）
Y=F, Cl in the formula ,-OSO
2F or-OSO
2Cl preferentially selects F for use.Reaction be based on the reaction formula of bottom (with K
2CO
3Be alkali):
The productive rate of the method for mentioning by this method gained productive rate and top of applying for a patent is same grade, with initial aceto-acetamide be basic point be approximately theoretical value 20～90%.
Aceto-acetamide is got by for example acetoacetyl chlorine or diketene and ammonia effect, is a kind of common Industrial products.
The included compound of formula I has sulfonic acid fluoride SO
2F
2Chlorine sulfonic acid fluoride SO
2ClF, pyrosulfuryl fluorine FSO
2OSO
2F and chlorine pyrosulfuryl fluorine ClSO
2OSO
2F, the compound of preferentially selecting for use are sulfonic acid fluoride SO
2F
2
These sulfonic acid halides are made by currently known methods.SO for example
2F
2And SO
2ClF can be with SO
2Cl
2Be heated to about 60-80 ℃ with NaF and obtain ((JOrgChem) nineteen sixty the 25th is rolled up 2016 pages for CWTullock and DDCoffman, organic chemistry magazine).
In principle might provide alkali reaction material all can be used as alkali according to method of the present invention, but preferably reach the tertiary amine of 15 carbon atoms, also have oxide compound, oxyhydroxide and the acid carbonate of alkaline ion exchanger and basic metal and alkaline-earth metal in addition with sum.
The example of tertiary amine has: Trimethylamine 99, triethylamine, N-methyl Diisopropylamine, benzyldimethylamine, xylidine, N, N-lupetazin, N-ethylpiperidine, pyridine, α, β, γ-Pi Courlene, diaza-bicyclo octane, diaza-bicyclo undecane etc.
The alkaline ion exchanger that can use is commercial available product.
Be to can be used as the basic metal that example mentions and oxide compound, oxyhydroxide, carbonate and the acid carbonate of alkaline-earth metal below:
LiOH、Li
2CO
3、LiHCO
3
NaOH、Na
2CO
3、NaHCO
3
KOH、K
2CO
3、KHCO
3
CaO Ca(OH)
2, CaCO
3, Ca(HCO
3)
2Deng
Gratifying especially alkali is that sum only is the tertiary amine of 10 carbon atoms and the oxide compound and the carbonate of potassium and sodium.K
2CO
3Good especially, because of making A Saisuofa wood potassium, it obtains with a kind of much easy way.
The use of uniting of several alkali also is fine, for example earlier with a kind of tertiary amine thereupon again with a kind of alkali metal hydroxide effect.
According to method of the present invention, the S-O compound of aceto-acetamide and formula I is about 1 with mol ratio: (1-1.5) use better; For making cyclisation complete, every mole of aceto-acetamide at least will be with about 3 equivalent alkali, preferably 3-5 equivalent.So just obtained 2 of salt formula, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone, available in case of necessity usual way obtains acd compound by salt, for example uses ore deposit acid (hydrochloric acid, sulfuric acid etc.), acid-salt (KHSO
4Deng) or acid ion exchangers.
According to the present invention, be reflected at or carried out when not having inert solvent and thinner, just the sort of solvent and the thinner that under reaction conditions, does not react in undesirable mode with starting raw material and final product.
The organic solvent of proton transfer or non-proton transitivity all suits, lower alcohol (methyl alcohol for example, ethanol, Virahol, the trimethyl carbinol etc.), lower aliphatic hydrochloric ether (ethylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, zellon etc.), fragrance hydrochloric ether (chlorobenzene, chlorotoluene etc.), ketone (acetone, methylethylketone, the ring ethyl ketone, methyl phenyl ketone etc.) aliphatic carboxylic acid fat (ethyl acetate, butylacetate, methyl propionate, diethyl malonate, Succinic acid dimethylester, the acetate methoxyethyl ester, ethylene glycol acetate, glycol diacetate, ethyl cyanoacetate etc.), aromatic carboxylates's (methyl benzoate, ethyl benzoate etc.), aliphatic amide (dimethyl formamide, N,N-DIMETHYLACETAMIDE etc.), urea derivative (tetramethyl-urea, tetrabutyl urea etc.) and aliphatics and aromatics nitrile (acetonitrile, cyanobenzene etc.).
Solvent and thinner can use separately or intermingling uses (even in scope of miscibility gap).
Use inorganic solvent also to be fine for example liquid SO
2, also used water when suitable.If but chlorinated products and pyrosulfuryl fluorine can not waters during as the compound of formula I, because they are easy to water and hydrolytic action takes place soon.Sulfonic acid fluoride is stable to water, is like this when temperature is not too high at least.
Satisfied solvent is that acetonitrile and aqueous acetone, especially water-content are the aqueous acetone of the 1-12% of weight ratio.
The amount of solvent and thinner is not very strict in principle, should determine the degree that is easy to stir at reaction mixture.The upper limit amount of solvent and thinner depends mainly on economic consideration, and rare excessively solution no longer is favourable.
Temperature of reaction also can change in quite wide scope.Reaction can approximately-70 ℃ carry out between the boiling point of solvent or thinner, this depends on the selection of alkali and solvent or thinner.Speed of response can slow down under lower temperature, and productive rate can reduce under too high temperature.Usually, general temperature range is at-70 ℃ to+100 ℃ approximately, preferably make an appointment with-10 and+60 ℃ between.
Though depress also and can react adding, best reaction pressure is normal atmosphere normally, decompression is little suitable.
React according to the present invention, say that in principle it is possible that the reactive component that enters reactor with any order or while is continuously measured.A kind of embodiment of superiority is to introduce aceto-acetamide and alkali, is dissolved in the S-O compound of a kind of inert solvent or thinner and metering-type I in the time of suitably.
Reaction mixture is checked with usual method.
The present invention has tangible economic worth, because the raw material simple reaction is carried out and high yield in some cases easily.
Now the present invention is described in detail with following embodiment.
Embodiment 1
10,1 gram (0.1 mole) aceto-acetamide and 33.0 gram (0.33 mole) triethylamines are dissolved in 100 milliliters of acetonitriles, put to the round-bottomed flask that agitator and solidified carbon dioxide condenser are housed, restrain (0.1 mole) sulfonic acid fluoride gases under-70 ℃ with 10.2 then, feed in 30 minutes.
With reaction mixture restir 3 hours subsequently, be allowed to warm to room temperature during this.It is dropped in 90 milliliters of 4NKOH methanol solutions then, suction filtration goes out reaction product.Obtain 7.2 gram (theoretical value 36%) A Saisuofa wood potassium, the infrared spectra qualification result is identical with reliable material.
Embodiment 2
As example 1, with 10.1 gram (0.1 mole) aceto-acetamides, 50.5 gram (0.5 mole) triethylamines and 100 milliliters of acetonitriles are put to one and are equipped with in the round-bottomed flask of agitator and solidified carbon dioxide water cooler.In 20 minutes, feed 15.3 gram (0.15 mole) sulfonic acid fluoride gases, reactant is warm down to room temperature in stirring.Stir after 2 hours, 230 milliliters of (0.46 mole) 2NKOH methanol solutions are splashed into, suction filtration goes out product.Obtain 9.7 gram (theoretical value 48%) A Saisuofa wood potassium.
Embodiment 3
With a cumulative volume 50 milliliters 40.4 gram (0.4 mole) triethylamine and liquid SO
2Mixture drip to 70 milliliters of liquid SO in-10 ℃
2Contain in the solution of 20.2 gram (0.2 mole) aceto-acetamides and 23.7 gram (0.2 mole) chlorine sulfonic acid fluoride.This mixture stirred 2 hours, steamed liquid SO then
2, under vacuum, handle at last.Residue drops in 400 milliliters of NaOH aqueous solution, with the concentrated hydrochloric acid acidifying, with ice-cooled, uses ethyl acetate extraction.Ethyl acetate is with gac and Na
2SO
4After the processing, the extracting solution vaporising under vacuum.Obtain 15 grams (almost be theoretical value 20%) 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone.
Embodiment 4
The water of different amounts adds in 150 milliliters of acetone.10.1 gram (0.1 mole) aceto-acetamide and 69 gram (0.5 mole) finely powdered are done K
2CO
3Add in each aqueous mixture.Feed 13.5 gram (0.15 mole) sulfonic acid fluoride gases, at room temperature carry out, the temperature of reaction mixture rises to about 40 ℃ in the venting process, restir 2 hours, and bleeding leaches product.Filter residue contains A Saisuofa wood potassium, and (silica gel, solvent system: ethyl acetate/Glacial acetic acid (5: 1) check is identical with reference sample through thin-layer chromatography.Filter residue changes in the mixture of ice and excessive hydrochloric acid, with ethyl acetate extraction.Acetic acid ethyl acetate extract is with Na
2SO
4Doing the baking back evaporates under vacuum.Obtain crystalline 2,2-titanium dioxide 6-methyl-3,4-dihydro-1,2,3-Evil thiazine-4-ketone transfers this product to A Saisuofa wood potassium with the KOH methanol solution again.The results are shown in the following table.In the table in listed last experiment, K
2CO
3Be to use with 50% the aqueous solution.
Table
The productive rate of amount of water A Saisuofa wood potassium
With acetone is the percentage ratio of the theoretical value of benchmark
The milliliter gram
Weight percentage (%) (%)
0????-????3.75????23
2????1.7????10.86????67
6????5.1????12.15????75
8????6.7????14.10????86.5
10????8.4????12.20????75
12????10.1????11.54????71
14????11.8????8.3????51
69????58????6.4????39
Claims (7)
1, a kind ofly begins to prepare 2 by aceto-acetamide and S-O compound, 2-titanium dioxide 6-methyl-3,4-dihydro-1,2, the method of 3-Evil thiazine-4-ketone and non-toxic salt thereof is characterized in that comprising that aceto-acetamide and the S-O compound with formula I react in the presence of alkali
FSO
2Y (Ⅰ)
In the formula, Y=F, Cl ,-OSO
2F or-OSO
2Cl preferentially selects F for use.
2,, it is characterized in that wherein used alkali is oxide compound, oxyhydroxide, carbonate and the acid carbonate of rudimentary tertiary amine, alkaline ion exchanger and basic metal and alkaline-earth metal according to claim 1 described method.
3,, it is characterized in that wherein used alkali is the oxyhydroxide and the carbonate of rudimentary tertiary amine and sodium and potassium, especially only uses K according to claim 1 or 2 described methods
2CO
3
4,, it is characterized in that wherein every mole of aceto-acetamide will be with about 1-1.5 mole formula I S-O compound with at least about 3 equivalent alkali, preferably 3-5 equivalent alkali according to claim 1 described method.
5, according to claim 1 described method, it is characterized in that reacting in the presence of inert solvent or thinner and carry out, preferably in acetonitrile or aqueous acetone, especially water content is about 1-12%(weight) aqueous acetone in carry out.
6,, it is characterized in that reaction is to be about in temperature between-10 ℃ to+60 ℃ to carry out according to claim 1 described method.
7, according to claim 1 described method, it is characterized in that adding earlier aceto-acetamide and alkali (can suitably be dissolved in inert solvent or the thinner), be metered into formula I S-O compound again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106284A CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2,2-dioxy 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-one and process for the preparation of its non-toxic salt |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843429039 DE3429039A1 (en) | 1984-08-07 | 1984-08-07 | METHOD FOR PRODUCING 6-METHYL-3,4-DIHYDRO-1,2,3-OXATHIAZINE-4-ON-2,2-DIOXIDE AND ITS NON-TOXIC SALTS |
| CN85106284A CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2,2-dioxy 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-one and process for the preparation of its non-toxic salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106284A CN85106284A (en) | 1987-02-18 |
| CN1007979B true CN1007979B (en) | 1990-05-16 |
Family
ID=25741973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106284A Expired CN1007979B (en) | 1984-08-07 | 1985-08-20 | 2,2-dioxy 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-one and process for the preparation of its non-toxic salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007979B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11718594B2 (en) | 2016-09-21 | 2023-08-08 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724994B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724993B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11731948B2 (en) | 2016-09-21 | 2023-08-22 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787001A (en) * | 2010-03-17 | 2010-07-28 | 广东省食品工业研究所 | Synthesis process of acesulfame potassium |
-
1985
- 1985-08-20 CN CN85106284A patent/CN1007979B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11718594B2 (en) | 2016-09-21 | 2023-08-08 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724994B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11724993B2 (en) | 2016-09-21 | 2023-08-15 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
| US11731948B2 (en) | 2016-09-21 | 2023-08-22 | Celanese International Corporation | Acesulfame potassium compositions and processes for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85106284A (en) | 1987-02-18 |
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