CN106008281A - New method for efficient preparation of camphorsulfonic acid - Google Patents

New method for efficient preparation of camphorsulfonic acid Download PDF

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Publication number
CN106008281A
CN106008281A CN201610380393.2A CN201610380393A CN106008281A CN 106008281 A CN106008281 A CN 106008281A CN 201610380393 A CN201610380393 A CN 201610380393A CN 106008281 A CN106008281 A CN 106008281A
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China
Prior art keywords
camphorsulfonic acid
new method
method efficiently
efficiently preparing
mixed gas
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CN201610380393.2A
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Chinese (zh)
Inventor
朱运涛
林韦康
高其
江晓明
刘凤能
归晨秋
丁芹
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ZHEJIANG YUNTAO BIOTECHNOLOGY CO Ltd
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ZHEJIANG YUNTAO BIOTECHNOLOGY CO Ltd
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Priority to CN201610380393.2A priority Critical patent/CN106008281A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a new method for efficient preparation of camphorsulfonic acid. Existing process has the disadvantages of: production cycle long to six days, large amount of waste acid, serious equipment corrosion, high labor insurance requirement, incomplete raw material reaction, and high cost. The method employs a mixed gas of sulfur trioxide and dried air or nitrogen to sulfonate synthetic camphor, and adopts dichloromethane, 1, 2-dichloroethane, petroleum ether, carbon tetrachloride, n-hexane, n-heptane and cyclohexane as the solvent. The invention employs the mixed gas of sulfur trioxide and dried air or nitrogen to sulfonate synthetic camphor, the volume ratio of sulfur trioxide is 5%-90%, preferably 10%, the solvent is preferably 1, 2-dichloroethane, and the sulfonation temperature ranges from -20DEG C to a boiling temperature of the adopted solvent, preferably 30DEG C. The method has the advantages of short production cycle, high yield, no generation of waste acid, and low cost.

Description

A kind of new method efficiently preparing camphorsulfonic acid
Technical field
The present invention relates to a kind of new method efficiently preparing camphorsulfonic acid.
Background technology
Existing process route: with artificial camphor as raw material, acetic anhydride is solvent and dehydrant, sulphuric acid or oleum For sulfonating agent artificial camphor sulfonic acid.Existing processing disadvantages: production cycle length to six day, spent acid amount is big, to setting Standby corrosivity is serious, requires higher to labour protection, and raw material reaction is the completeest, relatively costly.
Summary of the invention
The invention aims to solve above-mentioned technical problem, and provide a kind of and efficiently prepare the new of camphorsulfonic acid Method, the present invention is with short production cycle, and yield is high, and solvent, can meet almost without the three wastes with recovery Currently " Green Chemistry " theory.
The technical solution used in the present invention is: a kind of new method efficiently preparing camphorsulfonic acid, it is characterised in that with The gaseous mixture of sulfur trioxide and dry air or nitrogen carries out sulfonation to artificial camphor, with dichloromethane, 1,2- Dichloroethanes, petroleum ether, carbon tetrachloride, normal hexane, normal heptane, hexamethylene are solvent.
As preferably, in gaseous mixture, sulfur trioxide volume ratio is 5%-90%.
As preferably, described sulfur trioxide volume ratio is 10%.
As preferably, described solvent is 1,2-dichloroethanes.
As preferably, the temperature of sulfonation is-20 DEG C of boiling temperatures to employing solvent.
As preferably, the temperature of described sulfonation is-20 DEG C to 30 DEG C.
As preferably, by 1, the stirring of 2-dichloroethanes and artificial camphor is molten clearly, temperature control≤20 DEG C, logical SO3 with The mixed gas of dry air, sulfur trioxide volume ratio is 10%, to beginning with sour gas effusion, is cooled to ≤ 10 DEG C and be incubated 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
As preferably, by 1, the stirring of 2-dichloroethanes and artificial camphor is molten clearly, temperature control≤20 DEG C, logical SO3 with The mixed gas of nitrogen, sulfur trioxide volume ratio is 10%, to beginning with sour gas effusion, is cooled to≤10 DEG C And it being incubated 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
As preferably, by molten clearly with artificial camphor stirring for normal heptane, temperature control≤20 DEG C, logical SO3 and dry sky The mixed gas of gas, sulfur trioxide volume ratio is 15%, to beginning with sour gas effusion, is cooled to≤10 DEG C And it being incubated 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
As preferably, petroleum ether is molten clearly with artificial camphor stirring, temperature control≤20 DEG C, logical SO3 and dry air Mixed gas, sulfur trioxide volume ratio is 15%, to begin with sour gas effusion, be cooled to≤10 DEG C also Insulation 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
The present invention carries out sulfonation with the gaseous mixture of sulfur trioxide with dry air or nitrogen to artificial camphor.Three oxygen Changing sulfur volume ratio is 5%-90%, preferably 10%.With dichloromethane, 1,2-dichloroethanes, petroleum ether, tetrachloro Change carbon, normal hexane, normal heptane, hexamethylene etc. for solvent, preferably 1,2-dichloroethanes.Sulfonation temperature is-20 DEG C The extremely boiling temperature of employing solvent, preferably 30 DEG C.With short production cycle, yield is high, do not produce spent acid, cost Low.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Example 1
In 2000L reactor put into 1217kg 1,2-dichloroethanes, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 783.1kg Off-white color camphorsulfonic acid, molar yield 99.0%.
Example 2
In 2000L reactor put into 1217kg 1,2-dichloroethanes, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (5%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 766kg Camphorsulfonic acid, molar yield 96.8%.
Example 3
In 2000L reactor put into 1217kg 1,2-dichloroethanes, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (15%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 732kg Camphorsulfonic acid, molar yield 92.5%.
Example 4
In 2000L reactor put into 1217kg 1,2-dichloroethanes, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, logical SO3 escapes to beginning with sour gas with the mixed gas (10%SO3) of nitrogen.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 782.3kg Camphorsulfonic acid, molar yield 98.9%.
Example 5
In 2000L reactor put into 1205kg petroleum ether, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (5%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 717kg Camphorsulfonic acid, molar yield 90.6%.
Example 6
In 2000L reactor put into 1205kg petroleum ether, 518.5kg artificial camphor, stir molten clearly.Control Temperature≤20 DEG C, logical SO3 escapes to beginning with sour gas with the mixed gas (15%SO3) of dry air.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 735kg Camphorsulfonic acid, molar yield 93.0%.
Example 7
In 2000L reactor put into 1205kg petroleum ether, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 722kg Camphorsulfonic acid, molar yield 91.3%.
Example 8
In 2000L reactor put into 1205kg petroleum ether, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (10%SO3) of logical SO3 and drying nitrogen is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 727.7kg Camphorsulfonic acid, molar yield 92.0%.
Example 9
In 2000L reactor put into 1171kg normal heptane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (5%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 746kg Camphorsulfonic acid, molar yield 94.2%.
Example 10
In 2000L reactor put into 1171kg normal heptane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (15%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 755kg Camphorsulfonic acid, molar yield 95.5%.
Example 11
In 2000L reactor put into 1171kg normal heptane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 743.5kg Camphorsulfonic acid, molar yield 94.0%.
Example 11
In 2000L reactor put into 1171kg normal heptane, 518.5kg artificial camphor, stir molten clearly.Control Temperature≤20 DEG C, logical SO3 escapes to beginning with sour gas with the mixed gas (10%SO3) of dry air.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 739.6kg Camphorsulfonic acid, molar yield 93.5%.
Example 12
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (5%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 654kg Camphorsulfonic acid, molar yield 82.6%.
Example 13
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (15%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 672kg Camphorsulfonic acid, molar yield 85.0%.
Example 14
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤10 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 551kg Camphorsulfonic acid, molar yield 69.7%.
Example 15
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤0 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Effusion.
Insulation 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains 511kg camphorsulfonic acid, molar yield 64.6%.
Example 16
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤-10 DEG C, the mixed gas (10%SO3) of logical SO3 and dry air is to beginning with sour gas Body escapes.
Insulation 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains 458kg camphorsulfonic acid, molar yield 57.9%.
Example 17
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly. Temperature control≤-20 DEG C, logical SO3 escapes to beginning with sour gas with the mixed gas (10%SO3) of dry air Go out.
Insulation 1h, blowing is centrifuged, and room temperature in vacuo is dried, and obtains 411kg camphorsulfonic acid, molar yield 51.9%.
Example 18
In 2000L reactor put into 1245kg tetrachloromethane, 518.5kg artificial camphor, stir molten clearly.
Temperature control≤20 DEG C, the mixed gas (15%SO3) of logical SO3 and drying nitrogen is to beginning with sour gas Effusion.
Be cooled to≤10 DEG C and in≤10 DEG C be incubated 1h, blowing be centrifuged, room temperature in vacuo is dried, and obtains 681kg Camphorsulfonic acid, molar yield 86.1%.
The present invention that listed above is only is embodied as example, the invention is not restricted to above example, also Can there be many deformation.Those of ordinary skill in the art can directly derive from present disclosure or join The all deformation expected, are all considered as protection scope of the present invention.

Claims (10)

1. the new method efficiently preparing camphorsulfonic acid, it is characterised in that with sulfur trioxide and dry air or nitrogen Gaseous mixture artificial camphor is carried out sulfonation, with dichloromethane, 1,2-dichloroethanes, petroleum ether, four chlorinations Carbon, normal hexane, normal heptane, hexamethylene are solvent.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that gaseous mixture The volume ratio of middle sulfur trioxide is 5%-90%.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 2, it is characterised in that described The volume ratio of sulfur trioxide is 10%.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that described Solvent is 1,2-dichloroethanes.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 4, it is characterised in that sulfonation Temperature is-20 DEG C of boiling temperatures to employing solvent.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 5, it is characterised in that described sulphur The temperature changed is-20 DEG C to 30 DEG C.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that by 1,2- Dichloroethanes is molten clearly with artificial camphor stirring, temperature control≤20 DEG C, logical SO3 and the mixed gas of dry air, Sulfur trioxide volume ratio is 10%, to beginning with sour gas effusion, is cooled to≤10 DEG C and be incubated 1h, puts Material is centrifugal, and room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that by 1,2- Dichloroethanes is molten clearly with artificial camphor stirring, temperature control≤20 DEG C, logical SO3 and the mixed gas of nitrogen, three oxygen Changing sulfur volume ratio is 10%, to beginning with sour gas effusion, is cooled to≤10 DEG C and be incubated 1h, blowing from The heart, room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that by positive heptan Alkane is molten clearly with artificial camphor stirring, temperature control≤20 DEG C, logical SO3 and the mixed gas of dry air, three oxidations Sulfur volume ratio is 15%, to beginning with sour gas effusion, is cooled to≤10 DEG C and be incubated 1h, and blowing is centrifuged, Room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
A kind of new method efficiently preparing camphorsulfonic acid the most according to claim 1, it is characterised in that by oil Ether is molten clearly with artificial camphor stirring, temperature control≤20 DEG C, logical SO3 and the mixed gas of dry air, three oxidations Sulfur volume ratio is 15%, to beginning with sour gas effusion, is cooled to≤10 DEG C and be incubated 1h, and blowing is centrifuged, Room temperature in vacuo is dried, and obtains white camphorsulfonic acid.
CN201610380393.2A 2016-05-31 2016-05-31 New method for efficient preparation of camphorsulfonic acid Pending CN106008281A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369472A (en) * 2018-08-28 2019-02-22 河南慧锦药业有限公司 A kind of one kettle way preparation process of sodium camphorsulfonate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1228417A (en) * 1998-03-05 1999-09-15 福州大学 Method for preparing omega-d-camphoresulfonic acid
EP1036788A1 (en) * 1999-03-09 2000-09-20 Daicel Chemical Industries, Ltd. Process for producing sulfonic acids or salts thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1228417A (en) * 1998-03-05 1999-09-15 福州大学 Method for preparing omega-d-camphoresulfonic acid
EP1036788A1 (en) * 1999-03-09 2000-09-20 Daicel Chemical Industries, Ltd. Process for producing sulfonic acids or salts thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
柯春兰 等: "手性樟脑磺酸及其盐的合成与应用进展", 《江西化工》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369472A (en) * 2018-08-28 2019-02-22 河南慧锦药业有限公司 A kind of one kettle way preparation process of sodium camphorsulfonate

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Application publication date: 20161012