CN1066134C - New process for synthetising m-nitrobenzoic - Google Patents
New process for synthetising m-nitrobenzoic Download PDFInfo
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- CN1066134C CN1066134C CN98114154A CN98114154A CN1066134C CN 1066134 C CN1066134 C CN 1066134C CN 98114154 A CN98114154 A CN 98114154A CN 98114154 A CN98114154 A CN 98114154A CN 1066134 C CN1066134 C CN 1066134C
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- China
- Prior art keywords
- acid
- methyl
- methyl benzoate
- nitrobenzoate
- temperature
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- Expired - Fee Related
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- 238000000034 method Methods 0.000 title claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 28
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 238000010189 synthetic method Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- AXLYJLKKPUICKV-UHFFFAOYSA-N methyl 3-nitrobenzoate Chemical compound COC(=O)C1=CC=CC([N+]([O-])=O)=C1 AXLYJLKKPUICKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006396 nitration reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000010813 municipal solid waste Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000979 synthetic dye Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000975 dye Substances 0.000 description 2
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- QLZOWJNFLXSDSH-UHFFFAOYSA-N 4-methoxy-n-[[4-(trifluoromethyl)phenyl]methyl]butanamide Chemical compound COCCCC(=O)NCC1=CC=C(C(F)(F)F)C=C1 QLZOWJNFLXSDSH-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a novel synthetic method for preparing m-nitrobenzoic acid which is an important intermediate body in the chemical field of synthetic dye, medicines, etc. The method comprises: coarse methyl benzoate as a byproduct in the production process of dimethyl terephthalate as a polyester raw material is treated by sulfuric acid, is purified through crude distillation and then is nitrified by mixed acid of concentrated nitric acid and concentrated sulfuric acid, nitrified products are cooled, washed and separated to obtain methyl-m-nitrobenzoate, and then, the methyl-m-nitrobenzoate is hydrolyzed and neutralized by diluted alkali to obtain m-nitrobenzoic acid. With coarse methyl benzoate as raw material, the synthetic method has the characteristics of low cost, high yield, good product quality, etc. and is suitable for popularization.
Description
The present invention relates to a kind of synthetic method that is used to produce chemical field important intermediate M-NITROBENZOIC ACIDs such as synthetic dyestuff, medicine.
M-NITROBENZOIC ACID (m-NBA) is the important intermediate of Chemicals such as synthetic dyestuff, medicine, and its source is many to be oxidized to p-nitrobenzoic acid with para-nitrotoluene and to pay product and purify and produce m-NBA, and this kind method raw material sources are limited, the trouble of purifying, and cost is higher.English Patent 1519617 (1974) and 4288615 (1980) propose with the nitrated method of producing m-NBA of phenylformic acid, and its shortcoming is that acid consumption is big, and raw material is expensive, and transformation efficiency is on the low side.The disclosed nitrated method of producing methyl-m-nitrobenzoate (m-NBAE) and m-NBA of methyl benzoate (BME) of utilizing of China's Chemicals catalogues (1980J0124171 organic synthesis topical reference book), the working condition gentleness, yield is higher, but because of the source of BME producing after with methanol esterification from phenylformic acid, cost is also higher, so only can small serial production reagent.In addition, the method for producing m-NBA such as meta-nitrotoluene air oxidation process etc. also all is subjected to effects limit such as raw material, cost, can not apply.
The object of the present invention is to provide that a kind of cost is low, yield is high, the M-NITROBENZOIC ACID synthetic method of good product quality.
The present invention realizes like this.This kind synthetic method is utilized the by product crude methyl benzoate of polyester (PET) raw material dimethyl terephthalate (DMT) (DMT) production process, after vitriolization and rectification and purification, use concentrated nitric acid and vitriol oil mixed acid nitrification again, itrated compound is isolated methyl-m-nitrobenzoate through cooling, washing, make M-NITROBENZOIC ACID with diluted alkaline hydrolysis, neutralization again.
This synthetic method is implemented according to the following steps:
1, thick BME vitriolization.Adopt sulfuric acid or the oleum of concentration 80-98% (98% the best), under normal temperature to 60 ℃ temperature, thick BME is carried out acidifying.The sulfuric acid consumption is 2-30% (weight percent), decides according to foreign matter content, and mixing time can be 30 minutes one 24 hours.Extremely neutral with the frozen water washing then.
2, rectifying.BME after the acid treatment is placed in the rectifying tower, excision lower boiling p-Xylol (PX), water and high boiling material, the wherein positive fraction (197-201 ℃, normal pressure) of intercepting, BME purity can reach 95-99.5%.Rectifying can be operated under vacuum or normal pressure;
3, nitration reaction.With BME concentrated nitric acid and the vitriol oil mixed acid nitrification after purifying.Concentration of nitric acid is 65-99% (with 95% an above optimum) in the nitration mixture, sulfuric acid concentration 85-98% (98% the best) or oleum, and BME and nitration mixture proportioning (mol ratio) are: BME: HNO
3: H
2SO
4=1: 1: 0.5-1: 1.4: 2, nitrated temperature is-10-+30 ℃, nitrated time 1-4 hour.Nitrated mode: available a part of sulfuric acid bottoming, in reactor, add BME, drip nitration mixture again, also can adopt the mode that BME is dripped in nitration mixture:
4, cooling, washing, separation obtain thick m-NBAE.Nitration reaction liquid is poured into trash ice liquid or added temperature is in the water at low temperature of 0-15 ℃ (2-5 ℃ of the best), and m-NBAE is fully separated out.Isolate about 40% sulfuric acid and micro-nitric acid, filter cake cold water thorough washing obtains the wet product of thick m-NBAE;
5, with diluted alkaline hydrolysis, neutralization, make m-NBA.Adopt diluted alkaline (NaOH, KOH, the NH of concentration 5-20% (with 8% the best)
3), the m-NBAE crude product hydrolysis salify under 90-110 ℃ of (95-98 ℃ of the best) temperature with moisture 10-30% decolours with small amount of activated in case of necessity; Use (H again
2SO
4, HNO
3, HCL) to be neutralized to pH value in 20-70 ℃ of temperature range be 2-3; Filter the m-NBA solid, remove things such as inorganic salt with 30 ℃ of water washings, filter cake obtains flaxen m-NBA powder crystallization in vacuum, 60 ℃ of following dryings.
By product crude methyl benzoate during M-NITROBENZOIC ACID synthetic method provided by the invention is produced with the polyester raw material dimethyl terephthalate (DMT) is a raw material, has characteristics such as cost is low, yield is high, good product quality, is suitable for and applies.
Embodiment 1:
To specification is the sulfuric acid that adds 198 gram concentration 98% in the four-necked bottle stirred reactor of 1L earlier, under 15-16 ℃ of temperature, add 136 BMEs of gram through purifying, then, dropping restrains the nitric acid of concentration 95% and the nitration mixture that 67.5 sulfuric acid that restrain concentration 98% mix by 76.5, adds afterreaction 1 hour; Add 0-5 ℃ of cold water 250mL in reaction solution, the separate sulfur sour water is used 500L water washing filter cake more then, washes out a small amount of yellow oil; Filter cake is carried out dry 146 gram m-NBAE, 76 ℃ of its fusing points, content 96.5%, the yield 78.74% of getting under vacuum; Get 73 gram m-NBAE, to wherein adding 22 gram solid NaOH and 400mL water, at 98 ℃ of following alkaline hydrolysis; After oil reservoir disappears, add 3% gac and boiled 10 minutes, filter and obtain sodium salt liquid, use 30%H
2SO
4Being neutralized to pH value is 2, gets the m-NBA white precipitate; After the filtration, dry under vacuum and 66 ℃ of temperature with 300mL35 ℃ of water washing filter cake, m-NBA solid 56 grams, 140 ℃ of its fusing points, content 98.5%, m-NBA is 67.02% to the BME yield.
Embodiment 2:
Press embodiment 1 appointed condition, the sulfuric acid mixing back with 176 gram concentration 95% nitric acid and 418 gram concentration 98% adds in the reactor earlier, under agitation drips 340 gram BME then, nitration reaction under 10-15 ℃ of temperature; Handle by example 1, get 430 gram m-NBAE after the drying; Get 92 gram m-NBAE, adding 21 gram NaOH, 400mL water are handled by example 1 and are produced m-NBA, get 58.5 gram dry products after the drying.141 ℃ of its fusing points, content 98.0%, yield 71.02%.
Embodiment 3:
Make reflux with the 1L there-necked flask, get one-level industrial goods concentration and be 96% phenylformic acid 122 grams, add the sulfuric acid of 256 gram methyl alcohol and 2 gram concentration 98%, under 72-85 ℃ of temperature, refluxed 5 hours, remove methyl alcohol and water; NaHCO with concentration 5%
3In the aqueous solution and carboxylate to pH value be 7, tell and slightly heat up in a steamer BME and carry out rectifying, intercept 198-201 ℃ 126 restrain purification BME; Produce m-NBAE and m-NBA with this BME by example 1 method, obtain the m-NBA white powder at last.141.5 ℃ of its fusing points, yield 70.67%.
Claims (1)
1, a kind of M-NITROBENZOIC ACID synthetic method, it is characterized in that: this method is after utilizing the by product crude methyl benzoate process vitriolization and rectification and purification of polyester raw material dimethyl terephthalate (DMT) production process, use concentrated nitric acid and vitriol oil mixed acid nitrification again, itrated compound is isolated methyl-m-nitrobenzoate through cooling, washing, make a nitre phenyl formic acid with diluted alkaline hydrolysis, neutralization again; The implementation step of this synthetic method is as follows: A, crude methyl benzoate vitriolization adopt sulfuric acid or the oleum of concentration 80-98%, under normal temperature to 60 ℃ temperature, crude methyl benzoate is carried out acidifying, the sulfuric acid consumption is 2-30%, decide according to foreign matter content, mixing time is 30 minutes-24 hours, and is extremely neutral with the frozen water washing then; B, the rectifying methyl benzoate after with acid treatment places in the rectifying tower, excision lower boiling p-Xylol, water and high boiling material, and the wherein positive fraction of intercepting, rectifying is operated under vacuum or normal pressure; Methyl benzoate after C, nitration reaction will be purified concentrated nitric acid and vitriol oil mixed acid nitrification, concentration of nitric acid is 65-99% in the nitration mixture, and sulfuric acid concentration is 85-98% or oleum, and methyl benzoate and nitration mixture proportioning are methyl benzoate: HNO
3: H
2SO
4=1: 1: 0.5-1: 1.4: 2, nitrated temperature is-10-+30 ℃, nitrated time 1-4 hour, nitrated mode can add methyl benzoate with a part of sulfuric acid bottoming in reactor, drip nitration mixture again, also methyl benzoate can be dripped in nitration mixture; D, cooling, washing, separation, obtain thick methyl-m-nitrobenzoate, pouring nitration reaction liquid into trash ice liquid or adding temperature is in 0-15 ℃ the water, methyl-m-nitrobenzoate is fully separated out, isolate about 40% sulfuric acid and micro-nitric acid, filter cake cold water thorough washing obtains the wet product of thick methyl-m-nitrobenzoate; E, the hydrolysis of usefulness diluted alkaline, neutralization, make the diluted alkaline that a nitre phenyl formic acid adopts concentration 5-20%, methyl-m-nitrobenzoate crude product hydrolysis salify under 90-110 ℃ of temperature with moisture 10-30%, with the small amount of activated decolouring, being neutralized to pH value with acid under 20-70 ℃ of temperature again is 2-3, nitre phenyl formic acid solid between filtration in case of necessity, with 30 ℃ of water washings, remove inorganic salt, filter cake obtains a nitre phenyl formic acid powder crystallization in vacuum, 60 ℃ of following dryings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114154A CN1066134C (en) | 1998-07-14 | 1998-07-14 | New process for synthetising m-nitrobenzoic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114154A CN1066134C (en) | 1998-07-14 | 1998-07-14 | New process for synthetising m-nitrobenzoic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1203905A CN1203905A (en) | 1999-01-06 |
| CN1066134C true CN1066134C (en) | 2001-05-23 |
Family
ID=5223830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114154A Expired - Fee Related CN1066134C (en) | 1998-07-14 | 1998-07-14 | New process for synthetising m-nitrobenzoic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1066134C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859581A (en) * | 2016-04-21 | 2016-08-17 | 河间瀛州化工有限责任公司 | New nitration technology used in production of 2-cyano-4-nitro chlorobenzene |
| CN110143879B (en) * | 2019-04-29 | 2022-07-12 | 南京师范大学 | Device and method for recycling by-products generated in preparation of p-nitroacetophenone |
| CN113105323B (en) * | 2021-03-24 | 2022-07-19 | 江苏永安化工有限公司 | Green preparation process of 2-methyl-3-methoxybenzoyl chloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3978118A (en) * | 1975-07-11 | 1976-08-31 | Gulf Research & Development Company | Process for converting styrene or polystyrene to nitrobenzoic acids |
| GB1519602A (en) * | 1974-10-03 | 1978-08-02 | Bofors Ab | Preparing meta-nitrobenzoic acid |
-
1998
- 1998-07-14 CN CN98114154A patent/CN1066134C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1519602A (en) * | 1974-10-03 | 1978-08-02 | Bofors Ab | Preparing meta-nitrobenzoic acid |
| US3978118A (en) * | 1975-07-11 | 1976-08-31 | Gulf Research & Development Company | Process for converting styrene or polystyrene to nitrobenzoic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1203905A (en) | 1999-01-06 |
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