CN104649947A - Preparation method of 2,2'-dibenzamido diphenyl zinc disulfide - Google Patents
Preparation method of 2,2'-dibenzamido diphenyl zinc disulfide Download PDFInfo
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- CN104649947A CN104649947A CN201410812899.7A CN201410812899A CN104649947A CN 104649947 A CN104649947 A CN 104649947A CN 201410812899 A CN201410812899 A CN 201410812899A CN 104649947 A CN104649947 A CN 104649947A
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Abstract
The invention discloses a preparation method of a 2,2'-dibenzamido diphenyl zinc disulfide and belongs to the field of chemicals preparation, and the preparation method is used for solving the problems of complex process, high cost and dismal environmental protection of the process in the prior art for producing 2,2'-dibenzamido diphenyl zinc disulfide. The preparation method comprises the following steps: (1) ring-opening reaction; (2) acylation reaction; (3) salt forming reaction; and (4) zinc salt generating. According to the method, with cheap benzothiazole as a start raw material; after hydrolyzing to open ring, the product after acidifying directly reacts with benzoyl chloride in a water phase without using other organic solvent, the byproduct is inhibited by controlling the pH (potential of hydrogen) value of the reaction, the intermediate link is reduced by optimizing the process, the mother liquor is circulated, the synthesis method is simple and practicable, and is applicable to green industrial production. The melting point of the product obtained by the preparation method is 168-172 DEG C (the purity is high), and the yield is more than 90% according to benzothiazole.
Description
Technical field
The present invention relates to chemical preparing technical field, particularly one 2, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt.
Background technology
2,2'-dibenzoylamino diphenyl disulfide zinc salt is one of now widely used peptizer (world rubber industry, 2012(2), 1-5), it prepares usual method is be that starting raw material reduction disconnects S-S key and reacts with inorganic zinc salt with 2,2'-dibenzoylamino diphenyl disulfide; Or utilize near amino thiophenols and Benzoyl chloride to react to generate o-benzoyl aminothiophenol, regeneration 2,2'-dibenzoylamino diphenyl disulfide zinc salt.In reaction Raw 2, the 2'-dibenzoylamino diphenyl disulfide that relates to of a kind of method, S-S key is wanted first obtain (Wuhan University of Technology's journal, 2010,29(2) through oxidation above, 32-34), generate zinc salt and require again to disconnect, process does not have economy repeatedly; Simple but the control that reaction needed is stricter of rear a kind of procedure, when near amino thiophenols and Benzoyl chloride react and generate corresponding benzamide in addition, usually carry out in organic solvent or under organic base catalytic, as Wuhan University of Technology's journal (2010 in similar reaction, 29(2), 32-34) report employing chloroform give solvent.
Publication number discloses a kind of preparation method of rubber peptizer dibenzamidodiphenyl disulfide for the Chinese invention patent of " CN102304074A ", and it adopts triethylamine to make acid binding agent, and triethylamine is poisonous and have strong impulse.
2,2'-dibenzoylamino diphenyl disulfide zinc salt has important using value, but prior art not yet discloses the Green production method that low cost prepares 2,2'-dibenzoylamino diphenyl disulfide zinc salt.
Summary of the invention
2 are produced for solving in prior art, high and the problem not environmentally of 2'-dibenzoylamino diphenyl disulfide zinc salt complex process, cost, the invention provides that a kind of cost is low, the simple and Green production method of 2, the 2'-dibenzoylamino diphenyl disulfide zinc salts that productive rate is high of technique.
Technical scheme of the present invention is:
A kind of 2, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, comprises the following steps:
1) ring-opening reaction: take benzothiazole as starting raw material, under 110-120 DEG C of reflux conditions, benzothiazole open loop in the aqueous solution of sodium hydroxide obtains adjacent mercaptoaniline;
2) acylation reaction: adopt mineral acid regulating step 1 after cooling) pH of reaction soln is 8.8-9.2, under 5-10 DEG C of condition, drip Benzoyl chloride, after dropwising, holding temperature 5-10 DEG C, stirring reaction 0.5-3h, completes acidylate;
3) salt-forming reaction: to step 2) gained acidylate completes in liquid and drops into sodium hydroxide, and stir and be warming up to 70-80 DEG C, reaction 2-4h;
4) generate zinc salt: step 3) gained reaction solution is cooled to 40-50 DEG C, drop into zinc oxide, generate white precipitate, after completion of the reaction, separation and purification obtains 2,2 '-dibenzoylamino diphenyl disulfide zinc salt wet product;
5) oven dry, pulverizing, packaging get product.
Preferably, in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.0-2.2; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.0-1.1; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.0-1.1; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.5-0.6.
Further, in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.05-2.1; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.05-1.1; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.05-1.1; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.55-0.6.
Further, in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.1; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.05; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.05; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.55.
Preferably, in step 1), in aqueous sodium hydroxide solution, the weight of water is 2-3 times of sodium hydroxide weight, and reflux time is 2-3h.
Preferably, described in step 4), separation and purification is specially: centrifugation, washing purifying; Mother liquor and washing lotion is collected after separation and purification.
Further, the water available step 4 that in step 1), aqueous sodium hydroxide solution is used) in collect mother liquor and washing lotion substitute.
When the mother liquor collected in the pure water use step 4) in step 1) and washing lotion substitute, the quality of mother liquor and washing lotion is 3-3.5 times of pure water quality, take quality 3-3.5 doubly to mother liquor and the washing lotion of pure water, after steaming the water of mother liquor and washing lotion total mass 30%, then start back flow reaction.Wherein, the distilled water be steamed out can be used for the washings in step 4).
When the mother liquor collected in the pure water use step 4) in step 1) and washing lotion substitute, have white crystalline solid after ring-opening reaction terminates and separate out sodium formiate and sodium-chlor (supersaturation precipitation); Therefore; when the mother liquor collected in the pure water use step 4) in step 1) and washing lotion substitute; increase heat between ring-opening reaction and acylation reaction and consider operation (when 80-90 DEG C filtered while hot); the sodium-chlor of precipitation and sodium formiate are leached; a small amount of washing, filtrate and washing lotion enter acylation reaction operation.
Beneficial effect of the present invention is:
The invention provides a kind of 2, the preparation method of 2'-dibenzoylamino diphenyl disulfide zinc salt, reacts with the benzothiazole of cheapness for starting raw material, through hydrolysis, directly react at aqueous phase and Benzoyl chloride after product acidifying, not using other organic solvents, by controlling the pH value of reaction, suppressing by product to generate, pass through process optimization simultaneously, cut down the number of intermediate links, circulating mother liquor makes synthetic method simple, is applicable to green industrialized production.
The preparation method of 2,2'-dibenzoylamino diphenyl disulfide zinc salts of the present invention, product fusing point 168 DEG C-172 DEG C (purity is high), yield is (in benzothiazole) more than 90%.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is a kind of schema of the present invention 2,2'-dibenzoylamino diphenyl disulfide zinc salt preparation method;
Fig. 2 is the another kind of schema of the present invention 2,2'-dibenzoylamino diphenyl disulfide zinc salt preparation method.
Embodiment
Embodiment 1
As shown in Figure 1, concrete operation step is reaction process:
Drop into 170kg water, 84kg sodium hydroxide to 1000L with in the reactor of distillation and reflux, stir clearly molten, then input 135kg benzothiazole.Start to heat up, start when being warming up to 110 DEG C to occur backflow, temperature control 110 DEG C of-120 DEG C of back flow reaction 2 hours, ring-opening reaction completes.
Open loop liquid is transferred to another reactor, is cooled to 5 DEG C-10 DEG C, start to drip 30% hydrochloric acid, adjust pH=9, approximately spend 30% hydrochloric acid 12kg.Control temperature 5 DEG C-10 DEG C, drips 147kg Benzoyl chloride (rate of addition is 0.5-1L/min), along with the carrying out dripped, can find that there is yellow solid and generate, after dropwising, have a large amount of yellow solid, continue stirring reaction 1 hour, complete acidylate.
42kg sodium hydroxide is dropped into upper step acidylate and complete liquid, stir and be warming up to 70 DEG C-80 DEG C, will find that yellow solid dissolves gradually, react yellow solid after 2 hours and be dissolved.
Become salts solution to be cooled to 40 DEG C-50 DEG C upper step, drop into 75kg zinc chloride, a large amount of white solid can be found that there is and generate.Continue to be cooled to 25 DEG C-30 DEG C, blowing, centrifugation, filter cake 200kg purified water is washed.Collect filtrate and washing lotion altogether about 550kg treat down to criticize and recycle.Collecting filter cake is 2,2'-dibenzoylamino diphenyl disulfide zinc salt wet product, and weigh about 300kg.2,2'-dibenzoylamino diphenyl disulfide zinc salt 240kg is obtained after oven dry.Detect fusing point 172 DEG C, the about 92%(of yield is in benzothiazole).
Embodiment 2:
As shown in Figure 2, concrete operation step is reaction process:
To drop in embodiment 1 collected filtrate and washing lotion 550kg altogether to 1000L with in the reactor of distillation and reflux, drop into sodium hydroxide 84kg, stir clearly molten, then input benzothiazole 135kg.Heat up, start distillation, about 105 DEG C start to slip, and when steaming about 180kg water, reacting liquid temperature rises to 118 DEG C, stop distillation, start to carry out back flow reaction, keep reflux temperature 110 DEG C-120 DEG C, back flow reaction 2 hours.
After ring-opening reaction, can find, adularescent solid crystal is separated out.Be cooled to 80 DEG C-90 DEG C to be filtered by ring-opening reaction liquid while hot, filtrate is transferred to another reactor, and a small amount of washing of filter cake, washing lotion is transferred to another reactor in the lump.Collect the mixture that filter cake is sodium-chlor and sodium formiate.Filtrate is cooled to 5 DEG C-10 DEG C, starts to drip 30% hydrochloric acid, adjusts pH=9, approximately spends 30% hydrochloric acid 11kg.Control temperature 5 DEG C-10 DEG C, drips 147kg Benzoyl chloride (rate of addition is 0.5-1L/min), along with the carrying out dripped, can find that there is yellow solid and generate, after dropwising, have a large amount of yellow solid, continue stirring reaction 1 hour, complete acidylate.
42kg sodium hydroxide is dropped into upper step acidylate and complete liquid, stir and be warming up to 70 DEG C-80 DEG C, will find that yellow solid dissolves gradually, react 2 hours yellow solids and be dissolved.
Salts solution is become to be cooled to 40 DEG C-50 DEG C upper step, drop into 75kg zinc chloride, a large amount of white solid can be found that there is generate, continue to be cooled to 25 DEG C-30 DEG C, blowing, centrifugation, filter cake 200kg(wherein has the water distilled out in 180kg step 1) purified water washing, collect filtrate and washing lotion altogether about 555kg treat down to criticize and recycle.Collecting filter cake is 2,2'-dibenzoylamino diphenyl disulfide zinc salt wet product, and weigh about 310kg.2,2'-dibenzoylamino diphenyl disulfide zinc salt 243kg is obtained after oven dry.Detect fusing point 170 DEG C, the about 93%(of yield is in benzothiazole).
Embodiment 3
As shown in Figure 1, concrete operation step is reaction process:
Drop into 510kg water, 250kg sodium hydroxide to 3000L with in the reactor of distillation and reflux, stir clearly molten, then input 405kg benzothiazole.Start to heat up, start when being warming up to 110 DEG C to occur backflow, temperature control 110 DEG C of-120 DEG C of back flow reaction 2 hours, ring-opening reaction completes.
Open loop liquid is transferred to another reactor, is cooled to 5 DEG C-10 DEG C, start to drip 30% hydrochloric acid, adjust pH=9, approximately spend 30% hydrochloric acid 36kg.Control temperature 5 DEG C-10 DEG C, drips 440kg Benzoyl chloride (rate of addition is 0.5-1L/min), along with the carrying out dripped, can find that there is yellow solid and generate, after dropwising, have a large amount of yellow solid, continue stirring reaction 1 hour, complete acidylate.
125kg sodium hydroxide is dropped into upper step acidylate and complete liquid, stir and be warming up to 70 DEG C-80 DEG C, will find that yellow solid dissolves gradually, react yellow solid after 2 hours and be dissolved.
Become salts solution to be cooled to 40 DEG C-50 DEG C upper step, drop into 225kg zinc chloride, a large amount of white solid can be found that there is and generate.Continue to be cooled to 25 DEG C-30 DEG C, blowing, centrifugation, filter cake 600kg purified water is washed.Collect filtrate and washing lotion altogether about 1650kg treat down to criticize and recycle.Collecting filter cake is 2,2'-dibenzoylamino diphenyl disulfide zinc salt wet product, and weigh about 905kg.2,2'-dibenzoylamino diphenyl disulfide zinc salt 720kg is obtained after oven dry.Detect fusing point 172.5 DEG C, the about 92%(of yield is in benzothiazole).
Embodiment 4:
As shown in Figure 2, concrete operation step is reaction process:
To drop in embodiment 3 collected filtrate and washing lotion 1650kg altogether to 3000L with in the reactor of distillation and reflux, drop into sodium hydroxide 250kg, stir clearly molten, then input benzothiazole 405kg.Heat up, start distillation, about 104 DEG C start to slip, and when steaming about 540kg water, reacting liquid temperature rises to 116 DEG C, stop distillation, start to carry out back flow reaction, keep reflux temperature 110 DEG C-120 DEG C, back flow reaction 2 hours.
After ring-opening reaction, can find, adularescent solid crystal is separated out.Be cooled to 80 DEG C-90 DEG C to be filtered by ring-opening reaction liquid while hot, filtrate is transferred to another reactor, and a small amount of washing of filter cake, washing lotion is transferred to another reactor in the lump.Collect the mixture that filter cake is sodium-chlor and sodium formiate.Filtrate is cooled to 5 DEG C-10 DEG C, starts to drip 30% hydrochloric acid, adjusts pH=9, approximately spends 30% hydrochloric acid 35kg.Control temperature 5 DEG C-10 DEG C, drips 445kg Benzoyl chloride (rate of addition is 0.5-1L/min), along with the carrying out dripped, can find that there is yellow solid and generate, after dropwising, have a large amount of yellow solid, continue stirring reaction 1 hour, complete acidylate.
125kg sodium hydroxide is dropped into upper step acidylate and complete liquid, stir and be warming up to 70 DEG C-80 DEG C, will find that yellow solid dissolves gradually, react 2 hours yellow solids and be dissolved.
Salts solution is become to be cooled to 40 DEG C-50 DEG C upper step, drop into 225kg zinc chloride, a large amount of white solid can be found that there is generate, continue to be cooled to 25 DEG C-30 DEG C, blowing, centrifugation, filter cake 600kg(wherein has the water distilled out in 540kg step 1) purified water washing, collect filtrate and washing lotion altogether about 1660kg treat down to criticize and recycle.Collecting filter cake is 2,2'-dibenzoylamino diphenyl disulfide zinc salt wet product, and weigh about 936kg.2,2'-dibenzoylamino diphenyl disulfide zinc salt 730kg is obtained after oven dry.Detect fusing point 171 DEG C, the about 93%(of yield is in benzothiazole).
Claims (7)
1. one kind 2, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that, comprise the following steps:
1) ring-opening reaction: take benzothiazole as starting raw material, under 110-120 DEG C of reflux conditions, benzothiazole open loop in the aqueous solution of sodium hydroxide obtains adjacent mercaptoaniline;
2) acylation reaction: adopt mineral acid regulating step 1 after cooling) pH of reaction soln is 8.8-9.2, under 5-10 DEG C of condition, drip Benzoyl chloride, after dropwising, holding temperature 5-10 DEG C, stirring reaction 0.5-3h, completes acidylate;
3) salt-forming reaction: to step 2) gained acidylate completes in liquid and drops into sodium hydroxide, and stir and be warming up to 70-80 DEG C, reaction 2-4h;
4) generate zinc salt: step 3) gained reaction solution is cooled to 40-50 DEG C, drop into zinc oxide, generate white precipitate, after completion of the reaction, separation and purification obtains 2,2 '-dibenzoylamino diphenyl disulfide zinc salt wet product;
5) oven dry, pulverizing, packaging get product.
2. as claimed in claim 12, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.0-2.2; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.0-1.1; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.0-1.1; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.5-0.6.
3. as claimed in claim 22, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.05-2.1; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.05-1.1; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.05-1.1; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.55-0.6.
4. as claimed in claim 32, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: in step 1), the mol ratio of benzothiazole and sodium hydroxide is 1:2.1; Step 2) in the add-on of Benzoyl chloride meet: the mol ratio of benzothiazole and Benzoyl chloride is 1:1.05; In step 3), the add-on of sodium hydroxide meets: the mol ratio of benzothiazole and sodium hydroxide is 1:1.05; In step 4), the add-on of zinc chloride meets: the mol ratio of benzothiazole and zinc chloride is 1:0.55.
5. as claimed in claim 12, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: in step 1), in aqueous sodium hydroxide solution, the weight of water be the 2-3 of sodium hydroxide weight doubly, reflux time is 2-3h.
6. as claimed in claim 12, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: separation and purification described in step 4) is specially: centrifugation, washing purifying; Mother liquor and washing lotion is collected after separation and purification.
7. as claimed in claim 62, the preparation method of 2 '-dibenzoylamino diphenyl disulfide zinc salt, is characterized in that: the water available step 4 that in step 1), aqueous sodium hydroxide solution is used) in the mother liquor collected and washing lotion substitute.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061272A (en) * | 2015-07-16 | 2015-11-18 | 山东阳谷华泰化工股份有限公司 | Preparation method of high-yield and low-cost peptizer DBD |
| CN115611788A (en) * | 2022-12-15 | 2023-01-17 | 吉林易渡化工有限公司 | Synthesis method of o-aminothiophenol |
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| CS256573B1 (en) * | 1986-08-28 | 1988-04-15 | Robert Poor | Method of diaminodiphenyldisulphide production |
| CN102153495A (en) * | 2011-02-28 | 2011-08-17 | 曹县思达化工有限公司 | Method for preparing rubber peptizer DBD |
| CN102304074A (en) * | 2011-06-21 | 2012-01-04 | 聊城大学 | Method for preparing rubber peptizing agent, namely 2,2'-dibenzamido diphenyl disulfide compound |
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| US3763199A (en) * | 1971-11-18 | 1973-10-02 | American Cyanamid Co | Process for preparing zinc 2-benzamido-thiophenate |
| CS256573B1 (en) * | 1986-08-28 | 1988-04-15 | Robert Poor | Method of diaminodiphenyldisulphide production |
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| D. RAMBABU 等: "AMBERLYST-15–CATALYZED SYNTHESIS OF 2-SUBSTITUTED 1,3-BENZAZOLES IN WATER UNDER ULTRASOUND", 《SYNTHETIC COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061272A (en) * | 2015-07-16 | 2015-11-18 | 山东阳谷华泰化工股份有限公司 | Preparation method of high-yield and low-cost peptizer DBD |
| CN115611788A (en) * | 2022-12-15 | 2023-01-17 | 吉林易渡化工有限公司 | Synthesis method of o-aminothiophenol |
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