CN1896055A - Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith - Google Patents
Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith Download PDFInfo
- Publication number
- CN1896055A CN1896055A CN 200510027679 CN200510027679A CN1896055A CN 1896055 A CN1896055 A CN 1896055A CN 200510027679 CN200510027679 CN 200510027679 CN 200510027679 A CN200510027679 A CN 200510027679A CN 1896055 A CN1896055 A CN 1896055A
- Authority
- CN
- China
- Prior art keywords
- acid
- phenyl disulfide
- salt
- cuprous
- formic acid
- 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.)
- Pending
Links
Abstract
Production of 2,-2,-diphenyl acid disulfide and its use are disclosed. The process is carried out by taking o-aminobenzoic acid as initial raw material, diazo reacting to obtain diazo salt, disulfide reacting diazo salt with inorganic salt sulfite, under the existence of catalyst to obtain the final product. It has higher recovery rate and purity. It can be used for benzisoquinoline ketone compound.
Description
Technical field:
The benzisothiazole ketone compounds that the present invention relates to the preparation method of 2-2 '-phenyl disulfide formic acid, particularly 2-2 '-phenyl disulfide formic acid and utilize this method to prepare.
Background technology:
The preparation of 2-2 '-phenyl disulfide formic acid (being called for short DTBA), traditional method (as document Org.Synth.1943, coll.vol 2,580) is to be starting raw material with the anthranilic acid, generate diazonium salt through diazotization reaction, carry out the curing reaction with sodium disulfide again and make.
Its typical operating procedure is:
In reactor, add anthranilic acid (99%) 2500 gram successively, pure water 8000 grams, the vitriol oil (95-98%) 1100 grams, stir evenly, be cooled to-5-5 ℃, then the Sodium Nitrite of 1300 grams 99% (be made into 30% the aqueous solution) is added in the feed liquid, finish, in 0-5 ℃ of insulation reflection 30 minutes, filter diazonium salt solution, stand-by.
Sodium sulphite 1400 grams of adding 61% in another reactor, 99% sulphur 380 restrains, and pure water 10000 restrains, and reaches 30% liquid caustic soda 150 and restrains, and is warming up to 60-100 ℃, reacts 40 minutes, and cooling, filtration get sodium disulfide solution.
In sodium disulfide solution, drip diazonium salt solution, keep warm 20-50 ℃ in material, finish, be incubated half an hour again, in 40-70 ℃ of adding sulfuric acid, regulate the Ph value then, separate out DTBA, filter, suitably wash filter cake, then oven dry to 4-5.Get DTBA 2650 grams, purity 83%.The molar yield of anthranilic acid is 80% relatively.
The recovery rate of this operational path is on the low side, and the DTBA purity that makes has only about 83%, has limited its application, needs further purification, and can increase equipment and operation like this, reduces recovery rate.Simultaneously, contain sodium sulphite and sodium polysulphide in this processing method waste water, for black collagen shape material, seriously polluted, more difficult.So generally speaking, the industrial production cost of this method is higher.
Summary of the invention:
The object of the present invention is to provide the preparation method of a kind of 2-2 '-phenyl disulfide formic acid, the recovery rate that solves prior preparation method is on the low side, and the DTBA purity that makes has only the technical problem about 83%, and utilizes method for preparing benzisothiazole ketone compounds.
For solving the problems of the technologies described above, the present invention is achieved in that
The preparation method of a kind of 2-2 '-phenyl disulfide formic acid, with the anthranilic acid is starting raw material, through diazotization reaction, generate diazonium salt, it is characterized in that: this diazonium salt and sulfurous attitude inorganic salt carry out the curing reaction and make 2-2 '-phenyl disulfide formic acid under catalyst action.
This diazotization reaction can be in hydrochloric acid or sulfuric acid medium, at-5-10 ℃, is reacted by anthranilic acid and sodium nitrite in aqueous solution, is incubated 5 to 70 minutes; One is 1 to 3 times of anthranilic acid for the mole dosage of acid, and one is 1 to 1.1 times of anthranilic acid for the mole dosage of nitrite.
The mole dosage that used sulfurous attitude inorganic salt are reacted in this curing be anthranilic acid 3.5-7 doubly; Catalyst system therefor comprises cuprous salt or cupric salt, and its mole dosage is 0.002-0.2 a times of anthranilic acid; And can add the basic metal salt compounded of iodine as cocatalyst, its mole dosage is 0.001-0.1 a times of anthranilic acid;
The curing reaction fs is that diazonium liquid and sulfurous attitude inorganic salt solution all are added dropwise in the aqueous solution that is dissolved with catalyzer and promotor, and during dropping, mixture warm maintains 20-50 ℃, finishes, and is warming up to 70-100 ℃, is incubated 0.5-3 hour; Then, regulate pH value to 3-6, filter, suitably wash filter cake, oven dry gets 2-2 '-phenyl disulfide formic acid.
These sulfurous attitude inorganic salt comprise sulphite, hydrosulphite, pyrosulfite, metabisulfite, or contain the formaldehyde sodium sulfoxylate of these salt.
This catalyzer comprises Tubercuprose, venus crystals, cuprous formate, cuprous acetate, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, copper sulfate, cuprous sulfate.
Potassiumiodide is as cocatalyst.
According to 2-2 '-phenyl disulfide formic acid that aforesaid method makes, the benzisothiazole ketone compounds of further prepared in reaction.
Embodiment:
Among the present invention,, be starting raw material with the anthranilic acid still,, generate diazonium salt, under catalyst action, carry out the curing reaction with sulfurous attitude inorganic salt again and make through diazotization reaction to the preparation of DTBA.
Processing parameter: diazotization reaction can be in hydrochloric acid or sulfuric acid medium, at-5-10 ℃, is reacted by anthranilic acid and sodium nitrite in aqueous solution, is incubated 5 to 70 minutes.One is 1 to 3 times of anthranilic acid for the mole dosage of acid, and one is 1 to 1.1 times of anthranilic acid for the mole dosage of nitrite.
Curing is reacted used sulfurous attitude inorganic salt and is comprised sulphite, hydrosulphite, and pyrosulfite, metabisulfite etc., or contain the material of these salt such as formaldehyde sodium sulfoxylate etc.The mole dosage of sulfurous attitude inorganic salt is 3.5-7 a times of anthranilic acid.Catalyst system therefor comprises cuprous salt or cupric salt, as Tubercuprose, venus crystals, cuprous formate, cuprous acetate, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, copper sulfate, cuprous sulfate etc., its mole dosage is 0.002-0.2 a times of anthranilic acid.And can add basic metal salt compounded of iodine (as potassiumiodide etc.) as cocatalyst, its mole dosage be anthranilic acid 0.001-0.1 doubly.
The curing reaction fs is that diazonium liquid and sulfurous attitude inorganic salt solution all are added dropwise in the aqueous solution that is dissolved with catalyzer and promotor, and during dropping, mixture warm maintains 20-50 ℃, finishes, and is warming up to 70-100 ℃, is incubated 0.5-3 hour.Then, regulate pH value to 3-6, filter, suitably wash filter cake, oven dry gets DTBA.
Use the DTBA recovery rate of method for preparing can reach about 90%, the purity height also can reach more than 95%, when using its preparation other products, does not need further purification, has reduced operation, has reduced cost.Simultaneously, do not contain sodium sulphite and sodium polysulphide in this processing method waste water, avoided pollution environment.
Embodiment 1: prepare DTBA with sodium bisulfite and composite catalyst
The anthranilic acid 2500 of adding 99% in reactor restrains successively, pure water 8000 grams, the vitriol oil (95-98%) 1100 grams, stir evenly, be chilled to-5-5 ℃, then the Sodium Nitrite of 1300 grams 99% (be made into 30% the aqueous solution) is added in the feed liquid, finish, in 0-5 ℃ of insulation reaction 30 minutes.Filter, get diazonium salt solution, stand-by.
The sodium bisulfite of 7300 grams 99.5% is dissolved in the 9000 gram water, stand-by.
60 gram cuprous chlorides (CP) and 30 gram potassiumiodides (CP) are dissolved in the 900 gram water, are warming up to 30-40 ℃, drip sodium sulfite solution and diazonium salt solution then, finish, be warming up to 80-90 ℃.Be incubated 1 hour, be cooled to 40 ℃, transfer pH value, filter, filter cake washing, oven dry to 4-5.Get DTBA 2600 grams, purity 96%.The molar yield of anthranilic acid is 90% relatively.
The yield of preparation DTBA is higher among the present invention, and (reaching about 90%), and product purity can be directly used in next step reaction up to more than 95%, need not refining the purification.The processing wastewater color and luster is lighter, and waste water is easy to biochemical treatment.This operational path relatively is fit to suitability for industrialized production.
With the DTBA that the inventive method makes, further reaction prepares the benzisothiazole ketone compounds, and such material general formula is as follows:
(R=hydrogen or alkyl, cycloalkyl or aryl)
Reaction process is as follows:
Embodiment 2: with DTBA (purity 96%) preparation 1, and 2-benzisothiazole-3-ketone (being called for short BIT)
333g DTBA (purity 96%) is added among the 2000mlCCl4 (CP), add SOCl2 (99%) 400g and DMF (CP) 10g again, backflow 8-12 hour, partially recycled solvent will expect that again temperature is chilled to 30-50 ℃.Feed about 80 gram chlorine in the feed back, be incubated half an hour, then the reaction material drop is added in the 1000g 28% nitrogen water, keep warm 30-50 ℃ in material.Finish, transfer pH value about 12 with NaOH, solvent is reclaimed in layering.The water layer crystallisation by cooling is separated out the BIT sodium salt.It is soluble in water, add acid to pH value 3-6, separate out BIT, dry as far as possible.Obtain BIT filter cake 356 grams of water content 20%.Analyzing its chemical purity through HPLC is 99.2%.DTBA calculates relatively, and its molar yield is 89%.
Embodiment 3, with DTBA (purity 83%) preparation BIT
Replace the DTBA of 333 gram purity 96% with the DTBA of 385 grams (purity 83%), all the other operations with
Embodiment 2 is identical.
At last, obtain BIT filter cake 330 grams of water content 20%, its chemical purity is 98.1% by analysis.Relative DTBA, its molar yield is 81%.
Being preferred embodiment of the present invention only in sum, is not to be used for limiting practical range of the present invention.Be that all equivalences of doing according to the content of the present patent application claim change and modification, all should be technology category of the present invention.
Claims (7)
1, the preparation method of a kind of 2-2 '-phenyl disulfide formic acid, with the anthranilic acid is starting raw material, through diazotization reaction, generate diazonium salt, it is characterized in that: this diazonium salt and sulfurous attitude inorganic salt carry out the curing reaction and make 2-2 '-phenyl disulfide formic acid under catalyst action.
2, the preparation method of 2-2 ' according to claim 1-phenyl disulfide formic acid, it is characterized in that: this diazotization reaction can be in hydrochloric acid or sulfuric acid medium, at-5-10 ℃, react by anthranilic acid and sodium nitrite in aqueous solution, be incubated 5 to 70 minutes; One is 1 to 3 times of anthranilic acid for the mole dosage of acid, and one is 1 to 1.1 times of anthranilic acid for the mole dosage of nitrite.
3, the preparation method of 2-2 ' according to claim 1 and 2-phenyl disulfide formic acid is characterized in that: the mole dosage that used sulfurous attitude inorganic salt are reacted in this curing be anthranilic acid 3.5-7 doubly; Catalyst system therefor comprises cuprous salt or cupric salt, and its mole dosage is 0.002-0.2 a times of anthranilic acid; And can add the basic metal salt compounded of iodine as cocatalyst, its mole dosage is 0.001-0.1 a times of anthranilic acid;
The curing reaction fs is that diazonium liquid and sulfurous attitude inorganic salt solution all are added dropwise in the aqueous solution that is dissolved with catalyzer and promotor, and during dropping, mixture warm maintains 20-50 ℃, finishes, and is warming up to 70-100 ℃, is incubated 0.5-3 hour; Then, regulate pH value to 3-6, filter, suitably wash filter cake, oven dry gets 2-2 '-phenyl disulfide formic acid.
4, the preparation method of 2-2 ' according to claim 3-phenyl disulfide formic acid is characterized in that: these sulfurous attitude inorganic salt comprise sulphite, hydrosulphite, pyrosulfite, metabisulfite, or contain the formaldehyde sodium sulfoxylate of these salt.
5, the preparation method of 2-2 ' according to claim 3-phenyl disulfide formic acid, it is characterized in that: this catalyzer comprises Tubercuprose, venus crystals, cuprous formate, cuprous acetate, cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, copper sulfate, cuprous sulfate.
6, the preparation method of 2-2 ' according to claim 3-phenyl disulfide formic acid, it is characterized in that: potassiumiodide is as cocatalyst.
7, the 2-2 ' that makes according to the described method of claim 1-phenyl disulfide formic acid, further the benzisothiazole ketone compounds of prepared in reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027679 CN1896055A (en) | 2005-07-12 | 2005-07-12 | Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027679 CN1896055A (en) | 2005-07-12 | 2005-07-12 | Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1896055A true CN1896055A (en) | 2007-01-17 |
Family
ID=37608729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510027679 Pending CN1896055A (en) | 2005-07-12 | 2005-07-12 | Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1896055A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037293A (en) * | 2015-06-04 | 2015-11-11 | 大丰跃龙化学有限公司 | Solid waste reutilization technique in BIT (1,2-benzoisothiazolyl-3-one) production |
| CN108816028A (en) * | 2018-07-27 | 2018-11-16 | 临沂华毅医药股份有限公司 | A kind of Matter Transfer for dithiodibenzoic acid utilizes device |
-
2005
- 2005-07-12 CN CN 200510027679 patent/CN1896055A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037293A (en) * | 2015-06-04 | 2015-11-11 | 大丰跃龙化学有限公司 | Solid waste reutilization technique in BIT (1,2-benzoisothiazolyl-3-one) production |
| CN108816028A (en) * | 2018-07-27 | 2018-11-16 | 临沂华毅医药股份有限公司 | A kind of Matter Transfer for dithiodibenzoic acid utilizes device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101941947B (en) | Synthesis method of 2-chloro-6-chloroquinoxaline | |
| CN1810780A (en) | Methylsulfonic acid preparing process | |
| CN113582812A (en) | Method for preparing chloroethylene by liquid phase catalysis | |
| CN1896055A (en) | Production of 2-2'-phenyl disulfide methanoic and benzisoquinoline ketone compound therewith | |
| CN1990460A (en) | Comprehensive treatment of glycine crystallization mother liquid | |
| CN111018757B (en) | Method for synthesizing 3-mercaptopropionic acid from acidic waste gas | |
| CN115974014A (en) | Preparation method of potassium bis (fluorosulfonyl) imide | |
| CN1295212C (en) | Reduction of 4,4'-diamino-diphenylethylene-2,2' disulfonic acid | |
| CN1057832A (en) | Preparation technique of diphenyl guanidine | |
| CN112604677B (en) | Catalyst, preparation method thereof and application thereof in preparation of nitroxide radical piperidinol | |
| CN1894205A (en) | Method for producing chlorosulfonyl isocyanate | |
| JP3789749B2 (en) | Method for producing thiosalicylic acid | |
| CN1224600C (en) | Method for reclaiming calcium oxalate from sewage comprising oxalic acid | |
| CN1616434A (en) | Method for producing 1,3-dimethyl -2-imidazolinone | |
| CN101805277B (en) | Preparation method of 2,2'-dithio-salicylic acid | |
| CN116768766A (en) | Preparation method of 4,4' -dichlorodiphenyl sulfone | |
| CN1226554A (en) | Production of 1,1'-bialkyl-dipyridines | |
| CN1289476C (en) | Method of preparing dimethyl thioether using methyl sodium sulphate | |
| CN1762942A (en) | A kind of preparation method for isodeca-deca-isoprene-yl alcohol | |
| CN1322684A (en) | Method of eliminating nitrogenous matters from hydrazine hydrate saline-alkali mud | |
| CN117209377B (en) | Continuous synthesis method of propionyl chloride | |
| CN1151124C (en) | Process for preparing N,N'-diphenyl sulfourea | |
| CN117924121A (en) | Synthetic method of CLT acid | |
| CN1247463C (en) | Method for preparing calcium chromate | |
| CN110343057B (en) | Synthesis method of amisulbrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |