CN101805277A - Preparation method of 2,2'-dithio-salicylic acid - Google Patents
Preparation method of 2,2'-dithio-salicylic acid Download PDFInfo
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- CN101805277A CN101805277A CN201010153714A CN201010153714A CN101805277A CN 101805277 A CN101805277 A CN 101805277A CN 201010153714 A CN201010153714 A CN 201010153714A CN 201010153714 A CN201010153714 A CN 201010153714A CN 101805277 A CN101805277 A CN 101805277A
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- Prior art keywords
- anthranilic acid
- acid
- liquid
- dithio
- catalyzer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims abstract description 82
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 48
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 26
- 239000012954 diazonium Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 11
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- 235000007715 potassium iodide Nutrition 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 229960004839 potassium iodide Drugs 0.000 claims description 8
- 235000009518 sodium iodide Nutrition 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 4
- 235000021050 feed intake Nutrition 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 241001062009 Indigofera Species 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- 241000220317 Rosa Species 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000010941 cobalt Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940059936 lithium bromide Drugs 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 229910052759 nickel Chemical group 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003426 co-catalyst Substances 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- AJQLEJAVGARHGQ-UHFFFAOYSA-N dithiosalicylic acid Chemical compound OC1=CC=CC=C1C(S)=S AJQLEJAVGARHGQ-UHFFFAOYSA-N 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 sulfate radical Chemical group 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000233855 Orchidaceae Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 2,2'-dithio-salicylic acid shown as the formula I, and the method comprises the following steps: taking o-aminobenzoic acid as raw material, using sodium nitrite and hydrochloric acid for carrying out diazotization at the temperature of 0-10 DEG C, obtaining diazotized solution, leading the diazotized solution to be reacted with liquid sulfur dioxide for 0.5-3 hours at the temperature of minus 20-minus 10 DEG C in the presence of a catalyst and a co-catalyst, then keeping the temperature at 80-100 DEG C for 0.5-2 hours, cooling, filtering and obtaining the 2,2'-dithio-salicylic acid. The preparation method has the advantages of high reaction yield, good product purity, simple separation, a small amount of produced waste water, low production cost and the like.
Description
(1) technical field
The present invention relates to a kind of 2, the preparation method of 2 '-dithio-salicylic acid.
(2) background technology
2,2 '-dithio-salicylic acid is called for short diacid, and chemical structural formula is suc as formula shown in the I; Molecular formula C
14H
10O
4S
2, molecular weight is 306.06; CAS accession number 119-80-2; Brown to pale powder; Fusing point: 288-290 ℃; Trade name: dithio-salicylic acid, dithiodibenzoic acid, DSTA are the important intermediate of a kind of medicine, dyestuff, sterilant BIT and light trigger ITX etc., and it is made an addition in coating and the tackiness agent, can improve the midew proof energy;
It is raw material that Chinese patent CN200510027679.4 once reported with the anthranilic acid, obtains target product, yield about 90% with the polysulfide reaction after diazotization.This technology will produce a large amount of unmanageable sulfur-containing waste waters, and environmental pollution is big.He Xianzhang reported with after the anthranilic acid diazotization with Na
2S9H
2O and sulfur reaction, yield be 90% (the Hangzhou chemical industry, 2000,30 (2), 14-18), and mention with after the anthranilic acid diazotization with SO
2Gas reaction prepares the method for dithiodibenzoic acid, and this method is because be diazonium liquid and SO
2Gas reaction belongs to the gas-liquid phase reaction, in the reaction process gas-liquid contact insufficient, a large amount of SO
2Gas has entered exhaust system, not only causes SO
2Service efficiency is very low, and has caused vent gas treatment will consume a large amount of alkali to neutralize, produce a large amount of waste water and waste residue, and environmental problem is serious.
(3) summary of the invention
The problem to be solved in the present invention provide a kind of simple to operate, production safety is reliable, reaction yield is high, production cost is low, eco-friendly 2, the synthetic method of 2 '-dithio-salicylic acid overcomes shortcomings such as product yield is low in the traditional technology, the factory effluent amount is big, the difficult purification of product.
The technical solution used in the present invention is as follows:
A kind of suc as formula 2 shown in the I, the preparation method of 2 '-dithio-salicylic acid, described method is: be raw material with the anthranilic acid, carrying out diazotization reaction with Sodium Nitrite and hydrochloric acid obtains diazonium liquid down at 0～10 ℃, and diazonium liquid is under-20～-10 ℃ of temperature, under the existence of catalyzer and promotor, with sulfur dioxide liquid reaction 0.5～3 hour, be incubated 0.5～2 hour down at 80～100 ℃ then, cooling, filtration obtains 2,2 '-dithio-salicylic acid; Described catalyzer is metal-salt M
mX
nIn one or more mixture, described M is copper, iron, cobalt or nickel, described X is chlorine, formate, acetate or sulfate radical, described m is valent absolute value of X, described n is valent absolute value of M, and described promotor is following one or more mixture: sodium iodide, potassiumiodide, magnesium iodide, lithium iodide, cuprous iodide, Sodium Bromide, Potassium Bromide, magnesium bromide, lithiumbromide, cupric bromide, iron bromide; Described anthranilic acid, Sodium Nitrite and HCl in the hydrochloric acid amount of substance ratio that feeds intake is 1.0: 1.0～1.5: 2.5～4.0; Described anthranilic acid and the sulfur dioxide liquid amount of substance ratio that feeds intake is 1.0: 1.5～5.0;
Described catalyzer is preferably following one or more mixture: cupric chloride, cuprous chloride, cuprous sulfate, copper sulfate, Tubercuprose, neutralized verdigris, iron protochloride, iron(ic) chloride, ironic formiate, iron acetate, cobalt chloride, rose vitriol, cobaltous formate, Cobaltous diacetate, nickelous chloride, nickel formate or nickel acetate, the more preferably mixture of one or more in the following compounds: copper sulfate, ferric sulfate, Cobaltous diacetate or nickel acetate.
Described promotor is preferably one or more the mixture in the following compounds: sodium iodide, potassiumiodide, Sodium Bromide or Potassium Bromide.
Described anthranilic acid, Sodium Nitrite and HCl in the hydrochloric acid amount of substance ratio that feeds intake is 1.0: 1.0～1.5: 2.5～4.0, be preferably 1.0: 1.1～1.2: 3.0～3.5, described anthranilic acid and the sulfur dioxide liquid amount of substance ratio that feeds intake is 1.0: 1.5～5.0, preferred 1.0: 2.0～3.0
The mass ratio that described anthranilic acid and catalyzer feed intake is 1.0: 0.01～0.10, be preferably 1.0: 0.02～and 0.03.
The mass ratio that described anthranilic acid and promotor feed intake is 1.0: 0.01～0.05, be preferably 1.0: 0.03～and 0.05.
Comparatively concrete, described 2,2 '-preparation method of dithio-salicylic acid comprises the steps: to add water in (1) reactor, anthranilic acid and hydrochloric acid, after the stirring and dissolving, carry out diazotization reaction at 0～10 ℃ of aqueous solution that drips Sodium Nitrite down, dropwise the back insulation reaction, tracking monitor to reaction finishes to obtain diazonium liquid; The mass percentage concentration 30～36% of described hydrochloric acid; (2) add entry, catalyzer and promotor in another reactor, add diazonium liquid and the sulfur dioxide liquid that step (1) obtains down at-20～-10 ℃, added the back insulation reaction 0.5～3 hour, be warming up to 80～100 ℃ of insulations 0.5～2 hour then, be cooled at last below 50 ℃, reacting liquid filtering obtains 2,2 '-dithio-salicylic acid.
In the described step (1), adding the amount of water and the anthranilic acid mass ratio that feeds intake in the reactor is 15～10: 1, preferred 6～7: 1.
In the described step (1), the mass percentage concentration of Sodium Nitrite is 10～30% in the aqueous solution of Sodium Nitrite, preferred 20～25%.
In the described step (2), adding the amount of water and the mass ratio of diazonium liquid is 0.05～0.5: 1, preferred 0.05～0.2: 1.
More specifically, of the present invention 2, the preparation method of 2 '-dithio-salicylic acid carries out according to following steps: add water in (1) reactor, the hydrochloric acid of anthranilic acid and mass percentage concentration 30%, after the stirring and dissolving, carry out diazotization reaction, react and test with potassium iodide starch test paper after 1～5 hour at 0～5 ℃ of aqueous solution that drips Sodium Nitrite down, test paper becomes orchid and promptly reacts end, obtains diazonium liquid; (2) add entry, catalyzer and promotor in another reactor, add diazonium liquid and the sulfur dioxide liquid that step (1) obtains down at-20～-10 ℃, added the back insulation reaction 1～2 hour, be warming up to 90～100 ℃ of insulations 1～1.5 hour then, be cooled to 40～45 ℃ at last, reaction is filtered and is obtained 2,2 '-dithio-salicylic acid; The HCl amount of substance ratio that feeds intake is 1.0: 1.1～1.2: 3.0～3.5 in described anthranilic acid, Sodium Nitrite and the hydrochloric acid, described anthranilic acid and the sulfur dioxide liquid amount of substance ratio that feeds intake is 1.0: 2.0～3.0, described anthranilic acid and the catalyzer mass ratio that feeds intake is 1.0: 0.02～0.03, and described anthranilic acid and the promotor mass ratio that feeds intake is 1.0: 0.03～0.05; Described catalyzer is one or more the mixture in the following compounds: copper sulfate, ferric sulfate, Cobaltous diacetate or nickel acetate; Described promotor is one or more the mixture in the following compounds: sodium iodide, potassiumiodide, Sodium Bromide or Potassium Bromide.In the described step (1), adding the amount of water and the anthranilic acid mass ratio that feeds intake in the reactor is 6～7: 1; In the described step (1), the mass percentage concentration of Sodium Nitrite is 20～25% in the aqueous solution of dropping Sodium Nitrite.In the described step (2), the mass ratio of the add-on of water and diazonium liquid is 0.4～0.6: 1.
Of the present invention 2,2 '-preparation method of dithio-salicylic acid, compared with prior art, advantage such as the present invention has reaction yield height, good product purity, separation is simple, factory effluent is few, production cost is low.The reaction of sulfurous gas liquid and diazonium liquid is belong to the homogeneous phase liquid phase reaction to this technology owing to adopted at low temperatures, two kinds of reactants all are liquid, contact very abundant, sulfurous gas utilization ratio height in the reaction process, amount of sulfur dioxide seldom in tail gas, not only reduced the usage quantity of sulfurous gas significantly, reduced the raw materials cost of product, and since in the tail gas sulfurous gas seldom be used for neutral alkali consumption and reduce, thereby waste water that produces and waste residue are seldom, environmental friendliness.
(4) embodiment:
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
(1) in 5000 liters of enamel reaction stills, adds 2800 liters in water, drop into 400 kilograms of (dry products of anthranilic acid, content 〉=99%, 2.89Kmol), open and stir, 800 liters of the technical hydrochloric acids (density 1.15kg/L) of adding 30% in still, be cooled to 0-5 ℃ with chilled brine, in still, drip by 222 kilograms of Sodium Nitrite (dry products, content 〉=99% 3.19Kmol) and the solution formed of 600 kg of water, react after 2 hours iodine usefulnessization potassium starch test paper and tests, test paper becomes indigo plant and promptly reacts end, obtains about 4500 kilograms of diazonium liquid.(2) in reactor, add 300 kg of water, 5 kilograms of potassiumiodides and 6 kilograms of copper sulfate, be cooled to-10 ℃, 370 kilograms of sulfur dioxide liquids (5.78Kmol) and above-mentioned diazonium liquid are slowly added, add back insulation 2 hours, be warming up to 100 ℃ of insulations and be cooled to 40 ℃ after 1 hour, filtration, drying, obtain 2,432.4 kilograms of 2 '-dithio-salicylic acids are 95.6% with the anthranilic acid rate of collecting, and are 97.8% through efficient liquid phase chromatographic analysis purity.Embodiment 2
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, chilled brine is cooled to 5-10 ℃, the charging capacity of Sodium Nitrite is 242 kilograms of (dry products, content 〉=99%, 3.47Kmol), 4 kilograms of sodium iodides and 8 kilograms of cuprous sulfates, the dropping temperature of diazonium liquid and sulfur dioxide liquid is-10 ℃, the sulfur dioxide liquid add-on is 555 kilograms, obtains 2,441.4 kilograms of 2 '-dithio-salicylic acids, with the anthranilic acid rate of collecting is 97.9%, is 98.1% through efficient liquid phase chromatographic analysis purity.
Embodiment 3
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, the charging capacity of Sodium Nitrite be 203 kilograms (dry product, content 〉=99%, 2.91Kmol), 4.5 kilogram potassiumiodide and 8 kilograms of neutralized verdigriss, 278 kilograms of sulfur dioxide liquids obtain 2,423.3 kilograms of 2 '-dithio-salicylic acids, with the anthranilic acid rate of collecting is 91.2%, is 95.3% through efficient liquid phase chromatographic analysis purity.
Embodiment 4
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, 30% technical hydrochloric acid charging capacity is 1250 liters in the step (1), the charging capacity of Sodium Nitrite is 302 kilograms of (dry products, content 〉=99%, 4.33Kmol), Sodium Nitrite is dissolved in 700 kg of water and obtains sodium nitrite in aqueous solution, add 2200 kg of water, 8 kilograms of magnesium iodides in the step (2), 10 kilograms of copper sulfate and 12 kilograms of nickelous chlorides, 925 kilograms of sulfur dioxide liquids, obtain 2,441.4 kilograms of 2 '-dithio-salicylic acids are 98.6% with the anthranilic acid rate of collecting, and are 98.8% through efficient liquid phase chromatographic analysis purity.
Embodiment 5
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, 2 kilograms of sodium iodides, 2 kilograms of Sodium Bromides, 6 kilograms of ferric sulfate and 10 kilograms of cobaltous formates, 740 kilograms of sulfur dioxide liquids, obtain 2,429.7 kilograms of 2 '-dithio-salicylic acids are 93.3% with the anthranilic acid rate of collecting, and are 96.1% through efficient liquid phase chromatographic analysis purity.
Embodiment 6
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, 2 kilograms of cuprous iodides, 4 kilograms of iron bromides, 6 kilograms of cuprous chlorides and 12 kilograms of nickel acetates, 555 kilograms of sulfur dioxide liquids, obtain 2,470.0 kilograms of 2 '-dithio-salicylic acids are 86.6% with the anthranilic acid rate of collecting, and are 81.5% through efficient liquid phase chromatographic analysis purity.
Embodiment 7
Preparation process is identical substantially with the method for embodiment 1, difference from Example 1 is, 2 kilograms of lithium iodides, 4 kilograms of lithiumbromides, 6 kilograms of neutralized verdigriss and 12 kilograms of nickel formates, 555 kilograms of sulfur dioxide liquids, obtain 2,452.3 kilograms of 2 '-dithio-salicylic acids are 81.3% with the anthranilic acid rate of collecting, and are 79.5% through efficient liquid phase chromatographic analysis purity.
Embodiment 8
In 5000 liters of enamel reaction stills, add 2300 liters in water, drop into anthranilic acid 400 kilograms of (dry product, content 〉=99%, 2.89Kmol), open and stir, 1000 liters of the technical hydrochloric acids of adding 30% in still are cooled to 5-10 ℃ with chilled brine, in still, drip by 222 kilograms of Sodium Nitrite (dry products, content 〉=99% 3.19Kmol) and the solution formed of 600 kg of water, react after 10 hours iodine usefulnessization potassium starch test paper and tests, test paper becomes indigo plant and promptly reacts end, obtains 4522 kilograms of diazonium liquid.In reactor, add 1200 kg of water, 5 kilograms of potassiumiodides and 6 kilograms of copper sulfate, be cooled to-20 ℃, 370 kilograms of sulfur dioxide liquids (5.78Kmol) and above-mentioned diazonium liquid are slowly added, add back insulation 2 hours, be warming up to 80 ℃ of insulations and be cooled to 40 ℃ after 1 hour, filtration, drying, obtain 2,383.13 kilograms of 2 '-dithio-salicylic acids are 72.5% with the anthranilic acid rate of collecting, and are 83.7% through efficient liquid phase chromatographic analysis purity.
Claims (9)
1. one kind suc as formula 2 shown in the I, the preparation method of 2 '-dithio-salicylic acid, it is characterized in that described method is: be raw material with the anthranilic acid, carrying out diazotization reaction with Sodium Nitrite and hydrochloric acid obtains diazonium liquid down at 0～10 ℃, and diazonium liquid is under-20～-10 ℃ of temperature, under the existence of catalyzer and promotor, with sulfur dioxide liquid reaction 0.5～3 hour, be incubated 0.5～2 hour down at 80～100 ℃ then, cooling, filtration obtains 2,2 '-dithio-salicylic acid; Described catalyzer is metal-salt M
mX
nIn one or more mixture, described M is copper, iron, cobalt or nickel, described X is chlorine, formate, acetate or sulfate radical, described m is valent absolute value of X, described n is valent absolute value of M, and described promotor is following one or more mixture: sodium iodide, potassiumiodide, magnesium iodide, lithium iodide, cuprous iodide, Sodium Bromide, Potassium Bromide, magnesium bromide, lithiumbromide, cupric bromide, iron bromide; Described anthranilic acid, Sodium Nitrite and HCl in the hydrochloric acid amount of substance ratio that feeds intake is 1.0: 1.0～1.5: 2.5～4.0; Described anthranilic acid and the sulfur dioxide liquid amount of substance ratio that feeds intake is 1.0: 1.5～5.0;
2. the method for claim 1 is characterized in that described catalyzer is following one or more mixture: cupric chloride, cuprous chloride, cuprous sulfate, copper sulfate, Tubercuprose, neutralized verdigris, iron protochloride, iron(ic) chloride, ironic formiate, iron acetate, cobalt chloride, rose vitriol, cobaltous formate, Cobaltous diacetate, nickelous chloride, nickel formate or nickel acetate.
3. the method for claim 1, it is characterized in that described method comprises the steps: to add water in (1) reactor, anthranilic acid and hydrochloric acid, after the stirring and dissolving, carry out diazotization reaction at 0～10 ℃ of aqueous solution that drips Sodium Nitrite down, dropwise the back insulation reaction, tracking monitor to reaction finishes to obtain diazonium liquid; The mass percentage concentration 30～36% of described hydrochloric acid; (2) add entry, catalyzer and promotor in another reactor, add diazonium liquid and the sulfur dioxide liquid that step (1) obtains down at-20～-10 ℃, added the back insulation reaction 0.5～3 hour, be warming up to 80～100 ℃ of insulations 0.5～2 hour then, be cooled at last below 50 ℃, reacting liquid filtering obtains 2,2 '-dithio-salicylic acid.
4. as the described method of one of claim 1～3, it is characterized in that the mass ratio that described anthranilic acid and catalyzer feed intake is 1.0: 0.01～0.10.
5. as the described method of one of claim 1～3, it is characterized in that the mass ratio that described anthranilic acid and promotor feed intake is 1.0: 0.01～0.05.
6. method as claimed in claim 3 is characterized in that in the described step (1), and adding the amount of water and the anthranilic acid mass ratio that feeds intake in the reactor is 5～10: 1.
7. method as claimed in claim 3 is characterized in that in the described step (1), and the mass percentage concentration of Sodium Nitrite is 10～30% in the aqueous solution of dropping Sodium Nitrite.
8. method as claimed in claim 3 is characterized in that in the described step (2), the mass ratio of the add-on of water and diazonium liquid is 0.05～0.5: 1.
9. the method for claim 1, it is characterized in that described method comprises the steps: to add water in (1) reactor, the hydrochloric acid of anthranilic acid and mass percentage concentration 30%, after the stirring and dissolving, carry out diazotization reaction at 0～5 ℃ of aqueous solution that drips Sodium Nitrite down, react after 1～5 hour and test with potassium iodide starch test paper, test paper becomes indigo plant and promptly reacts end, obtains diazonium liquid; (2) add entry, catalyzer and promotor in another reactor, add diazonium liquid and the sulfur dioxide liquid that step (1) obtains down at-20～-10 ℃, added the back insulation reaction 1～2 hour, be warming up to 90～100 ℃ of insulations 1～1.5 hour then, be cooled to 40～45 ℃ at last, reaction is filtered and is obtained 2,2 '-dithio-salicylic acid; Described anthranilic acid, Sodium Nitrite and HCl in the hydrochloric acid amount of substance ratio that feeds intake is 1.0: 1.1～1.2: 3.0～3.5, described anthranilic acid and the sulfur dioxide liquid amount of substance ratio that feeds intake is 1.0: 2.0～3.0, described anthranilic acid and the catalyzer mass ratio that feeds intake is 1.0: 0.02～0.03, and described anthranilic acid and the promotor mass ratio that feeds intake is 1.0: 0.01～0.02; Described catalyzer is one or more the mixture in the following compounds: copper sulfate, ferric sulfate, Cobaltous diacetate or nickel acetate; Described promotor is one or more the mixture in the following compounds: sodium iodide, potassiumiodide, Sodium Bromide or Potassium Bromide.
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| 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 |
| CN111518003A (en) * | 2020-05-26 | 2020-08-11 | 东营市金凤凰化工股份有限公司 | Purification method of dithiodibenzoic acid |
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| 《杭州化工》 20001231 贺贤璋 2,2'-二硫代二苯甲酸的制备 第14-18页 1-9 第30卷, 第2期 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111518003A (en) * | 2020-05-26 | 2020-08-11 | 东营市金凤凰化工股份有限公司 | Purification method of dithiodibenzoic acid |
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