CN107473971A - Benzoyl cyanide synthesizes the new technology of methyl benzoylformate - Google Patents
Benzoyl cyanide synthesizes the new technology of methyl benzoylformate Download PDFInfo
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- CN107473971A CN107473971A CN201710861474.9A CN201710861474A CN107473971A CN 107473971 A CN107473971 A CN 107473971A CN 201710861474 A CN201710861474 A CN 201710861474A CN 107473971 A CN107473971 A CN 107473971A
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- benzoyl cyanide
- methyl benzoylformate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
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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
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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Abstract
The invention discloses a kind of new technology of benzoyl cyanide synthesis methyl benzoylformate, comprise the following steps：Benzoyl cyanide is dissolved in organic solvent, halide catalyst and phase transfer catalyst is added, the concentrated sulfuric acid is added dropwise in system through 5~60min at 5 DEG C~20 DEG C, 0.5~5h of insulation reaction obtains intermediate imine base sulfate compound at 20~40 DEG C；Methanol is added dropwise in system through 5~60min at 30~50 DEG C, methyl benzoylformate is obtained after 0.5~5h of insulation reaction at 50~100 DEG C.By the present invention in that making low-temp reaction speed substantially accelerate with suitable solvent and composite catalyst, potential safety hazard present in industrialized production is eliminated, improves the stability of production, reduces energy consumption, and high income is up to 96%.
Description
Technical field
The present invention relates to field of fine chemical, in particular to a kind of new work of benzoyl cyanide synthesis methyl benzoylformate
Skill.
Background technology
Methyl benzoylformate is the compound containing carbonyl, carboxylic acid group and ester group, due to multiple active groups, table
Reveal special property, important bioactive compound can be synthesized, be commonly used for organic synthesis, light trigger, be medicine, agriculture
A kind of important intermediate in medicine synthesis.
The production method of methyl benzoylformate mainly uses benzoyl cyanide as raw material at present, further acidolysis, esterification
Obtain methyl benzoylformate.Raw material benzoyl cyanide fusing point is 29~32 DEG C in the process route, and easily solidification is unfavorable under low temperature
The progress of reaction；The intermediate product imido grpup sulfuric ester of generation violent crystallization exotherm, viscous wall, short time can ask material solidification etc.
, great potential safety hazard be present, be unfavorable for industrialized production in topic.
Nantong De Hexi Chemical Co., Ltd.s solve benzoyl cyanide low-temperature setting by adding solvent methyl benzoate and asked
Topic, but recycling design high energy consumption in post processing, and yield is low (88~90%).
There is the mobility that company solves intermediate product imido grpup sulfuric ester building-up process by increasing the proportioning of the concentrated sulfuric acid
Problem, but caused spent acid water greatly increases, and yield is low (85~88%).
Therefore, it is necessary to develop a kind of new work of the benzoyl cyanide synthesis methyl benzoylformate of high income and safety and environmental protection
Skill.
The content of the invention
Present invention aim to solve the deficiency of above-mentioned background technology, there is provided a kind of benzoyl cyanide synthesizes benzoyl first
The new technology of sour methyl esters, there is provided new organic solvent, introduce phase transfer catalyst, to solve safety existing for industrialization hidden
Suffer from, thus provide a kind of new technology of the lower benzoyl cyanide synthesis methyl benzoylformate of more practical, safety, cost.
The technical scheme is that：A kind of new technology of benzoyl cyanide synthesis methyl benzoylformate, it is characterised in that
Comprise the following steps：
A. benzoyl cyanide is dissolved in organic solvent, halide catalyst and phase transfer catalyst is added, by dense sulphur
Acid is added dropwise in system, and intermediate imine base sulfate compound is obtained after insulation reaction；
B. methanol is added dropwise in system, methyl benzoylformate is obtained after insulation reaction is complete.
In such scheme, halide catalyst is one kind in hydrogen chloride, ammonium chloride, sodium chloride, hydrogen bromide or sodium bromide
Or several combinations.It is preferred that ammonium chloride, so as to be advantageous to improve the yield of the invention reacted, reduces the generation of side reaction, high income
Up to 95%.
In such scheme, the phase transfer catalyst be polyethylene glycol, TBAB, triethyl benzyl ammonia chloride or
Three normal-butyl tetradecylphosphonium chlorides.It is preferred that triethyl benzyl ammonia chloride, exists so as to be advantageous to the inorganic anion group improved
Reactivity in organic phase, high income is up to 96%.
In such scheme, the organic solvent is toluene, dimethylbenzene or methyl benzoate.It is preferred that toluene, is carried for reactant
For the reacting environment of stable homogeneous.
Currently preferred technical scheme is：The dosage of organic solvent is 0.3~2 times of molar equivalent of benzoyl cyanide.Halogen
The dosage of compound catalyst is 0.01~0.13 times of molar equivalent of benzoyl cyanide.The dosage of phase transfer catalyst is benzoyl cyanide
0.002~0.01 times of molar equivalent.The dosage of methanol is 0.5~4 times of molar equivalent of benzoyl cyanide.The dosage of the concentrated sulfuric acid is
1~5 times of molar equivalent of benzoyl cyanide.The concentration of the concentrated sulfuric acid is 60%~98%.Concentrated sulfuric acid concentration of the present invention is quality point
Number.
Currently preferred technical scheme is：The concentrated sulfuric acid is added dropwise in system through 5~60min at 5 DEG C~20 DEG C, 20
0.5~5h of insulation reaction obtains intermediate imine base sulfate compound at~40 DEG C.Will through 5~60min at 30~50 DEG C
Methanol is added dropwise in system, and methyl benzoylformate is obtained after 0.5~5h of insulation reaction at 50~100 DEG C.
Preferably technical scheme of the invention is：The dosage of organic solvent is 0.32~0.75 times mole of benzoyl cyanide and worked as
Amount；The dosage of halide catalyst is 0.01~0.13 times of molar equivalent of benzoyl cyanide；The dosage of phase transfer catalyst is benzene
0.0022~0.0023 times of molar equivalent of formyl cyanogen；The dosage of methanol is 1~2.47 times of molar equivalent of benzoyl cyanide；Dense sulphur
The dosage of acid is 1.11~1.47 times of molar equivalents of benzoyl cyanide；The concentration of the concentrated sulfuric acid is 85%~90%；Urged by two kinds
The precise match of dosage between agent, and the dosage of methanol and benzoyl cyanide coordinate, and are carried out at high speed reaction and selectivity is good, receipts
Rate is 90%~96%.
Technical scheme of the invention preferred is：
A. benzoyl cyanide is dissolved in toluene, adds ammonium chloride and TBAB, the concentrated sulfuric acid is added dropwise to body
Intermediate imine base sulfate compound is obtained in system, after insulation reaction；
B. methanol is added dropwise in system, and methyl benzoylformate is obtained after insulation reaction is complete.It is suitable that this programme uses
Solvent coordinates with composite catalyst makes low-temp reaction speed substantially accelerate, and insulation reaction 1 hour, methanol add after the concentrated sulfuric acid adds
Enter the methyl benzoylformate that rear 3 hours of insulation reaction obtain yield 95%.
Molar equivalent i.e. on the basis of benzoyl cyanide mole, for benzoyl cyanide rub by the mole of organic solvent in the present invention
0.5~2 times of that amount.Rest materials：Halide catalyst, phase transfer catalyst, methanol usage are similarly.
Beneficial effects of the present invention are：
1. by the present invention in that making low-temp reaction speed substantially accelerate with suitable solvent and composite catalyst, both solved
Benzoyl cyanide low-temperature setting influences the problem of reaction, also solves acutely to crystallize in intermediate imine base sulfuric ester building-up process and puts
The problems such as heat, viscous wall, short time make material solidification influence mobility, potential safety hazard present in industrialized production is eliminated, is carried
The high stability of production, reduces energy consumption, and high income is up to 96%.
2. the present invention moves to reaction in organic solvent, in the double action of halide catalyst and phase transfer catalyst
Under, make the inorganic anion group that participation is reacted that there is higher reactivity in organic phase, fast reaction under low temperature, and
It is the good, mild condition of selectivity, simple to operate.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
Into 500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 5.85g sodium chloride (0.01mol),
0.5g triethyl benzyl ammonia chlorides (0.0022mol), 60ml dimethylbenzene (0.49mol), it is maintained at 20 DEG C of dropwise addition 127.5g concentration
85% concentrated sulfuric acid 1 hour (1.11mol), it is warming up to 40 DEG C and is incubated 1 hour；It is small that 61ml methanol (1.51mol) 0.5 is added dropwise at 40 DEG C
When, it is warming up to 70 DEG C and is incubated 3 hours, stops reaction, steam methanol.Water 90g is added, separates sour water, water 160 is added into oil reservoir
Gram, washing twice, obtains crude product, rectification under vacuum obtains methyl benzoylformate 164.16g, content 90%, yield 90%.
Embodiment 2
The benzoyl cyanides of 133.8g 98% (1mol), 1g sodium bromides (0.01mol), 0.7g are added into 500mL reactor
TBAB (0.0022mol), 65ml toluene (0.75mol), it is maintained at 20 DEG C and the concentrated sulfuric acid of 127.5g concentration 85% is added dropwise
(1.11mol) 1 hour, it is warming up to 40 DEG C and is incubated 1 hour；85ml methanol (2.10mol) is added dropwise at 40 DEG C 1 hour, is warming up to 85
DEG C insulation 3 hours, stop reaction, steam methanol.Water 90g is added, separates sour water, 160 grams of water is added into oil reservoir, is washed twice,
Crude product is obtained, rectification under vacuum obtains methyl benzoylformate 165.94g, content 92%, yield 93%.
Embodiment 3
Into 500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 6.4g ammonium chlorides (0.012mol),
0.7g TBABs (0.0022mol), 67ml dimethylbenzene (0.54mol), it is dense to be maintained at 20 DEG C of dropwise additions, 160 grams of concentration 85%
Sulfuric acid (1.39mol) 1 hour, it is warming up to 40 DEG C and is incubated 1 hour；100ml methanol (2.47mol) is added dropwise at 40 DEG C 1.5 hours, rises
Warm to 90 DEG C are incubated 3 hours, stop reaction, steam methanol.Water 90g is added, separates sour water, 160 grams of water, washing are added into oil reservoir
Twice, crude product is obtained, rectification under vacuum obtains methyl benzoylformate 165.91g, content 94%, yield 95%.
Embodiment 4
Into 500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 6.4g ammonium chlorides (0.062mol),
0.08g sodium bromides (0.008mol), the normal-butyl tetradecylphosphonium chlorides (0.0023mol) of 1g tri-, 80g methyl benzoates
(0.59mol), it is maintained at 20 DEG C and 90% concentrated sulfuric acid (1.47mol) of 160g concentration is added dropwise 2 hours, is warming up to 40 DEG C and is incubated 1 hour；
40ml methanol (1mol) is added dropwise at 40 DEG C 0.5 hour, is warming up to 70 DEG C and is incubated 3 hours, stop reaction, steam methanol.Add water
90g, sour water is separated, into oil reservoir plus 160 grams of water, washing twice, obtain crude product, rectification under vacuum obtains methyl benzoylformate
166.1g, content 88%, yield 89%.
Embodiment 5
The benzoyl cyanides of 133.8g 98% (1mol), 7g sodium chloride (0.12mol), 1g bromines are added into 500mL reactor
Change sodium (0.01mol), 0.5g triethyl benzyl ammonia chlorides (0.0022mol), 40ml dimethylbenzene (0.32mol), be maintained at 20 DEG C
The 127.5g85% concentrated sulfuric acids (1.11mol) are added dropwise 1 hour, are warming up to 40 DEG C and are incubated 1 hour；61ml methanol is added dropwise at 40 DEG C
(1.51mol) 0.5 hour, it is warming up to 90 DEG C and is incubated 3 hours, stop reaction, steam methanol.Water 90g is added, separates sour water, to
In oil reservoir plus 160 grams of water, washing twice, obtain crude product, rectification under vacuum obtains methyl benzoylformate 165.9g, content
95%, yield 96%.
Embodiment 6
Into 500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 0.81g hydrogen bromides (0.01mol),
0.64g TBABs (0.002mol), 37ml dimethylbenzene (0.3mol), it is maintained at 5 DEG C of dropwise addition concentrated sulfuric acids of 163.3g 60%
(1mol) 40min, it is warming up to 20 DEG C and is incubated 0.5 hour；20.2ml methanol (0.5mol) is added dropwise at 30 DEG C 0.5 hour, is warming up to
50 DEG C are incubated 2 hours, stop reaction.Methanol is steamed, water 90g is added, separates sour water, 160 grams of water, washing two are added into oil reservoir
It is secondary, crude product is obtained, rectification under vacuum obtains methyl benzoylformate 162.1g, content 90%, yield 91%.
Embodiment 7
Into 500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 1.46g hydrogen chloride (0.04mol),
1g sodium bromides (0.01mol), the normal-butyl tetradecylphosphonium chlorides (0.004mol) of 1.74g tri-, 70ml toluene (0.8mol), keep
The concentrated sulfuric acids of 261.3g 75% (2mol) 5min is added dropwise at 10 DEG C, is warming up to 30 DEG C and is incubated 1 hour；40.4ml first is added dropwise at 30 DEG C
Alcohol (1mol) 5min, it is warming up to 50 DEG C and is incubated 5 hours, stop reaction, steam methanol.Water 90g is added, sour water is separated, to oil reservoir
In plus 160 grams of water, washing twice, obtain crude product, rectification under vacuum obtains methyl benzoylformate 165.7g, content 94%, receives
Rate 95%.
Embodiment 8
Into 1000mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 5.66g hydrogen bromides (0.07mol),
2.28g triethyl benzyl ammonia chlorides (0.01mol), 123ml dimethylbenzene (1mol), it is dense to be maintained at 15 DEG C of dropwise addition 367.5g 80%
Sulfuric acid (3mol) 1 hour, it is warming up to 40 DEG C and is incubated 2 hours；80.3ml methanol (2mol) 60min is added dropwise at 50 DEG C, is warming up to 50
DEG C insulation 3 hours, stop reaction, steam methanol.Water 90g is added, separates sour water, 160 grams of water is added into oil reservoir, is washed twice,
Crude product is obtained, rectification under vacuum obtains methyl benzoylformate 166.4g, content 92%, yield 93%.
Embodiment 9
Into 1500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 3.65g hydrogen chloride (0.1mol),
1.8g Macrogol 600s (0.003mol), 204g methyl benzoates (1.5mol), it is maintained at 20 DEG C of dropwise addition 98% dense sulphur of 400g
Acid (4mol) 50min, it is warming up to 30 DEG C and is incubated 3 hours；121.2ml methanol (3mol) is added dropwise at 30 DEG C 0.5 hour, is warming up to
100 DEG C are incubated 0.5 hour, stop reaction, steam methanol.Water 90g is added, separates sour water, 160 grams of water, washing are added into oil reservoir
Twice, crude product is obtained, rectification under vacuum obtains methyl benzoylformate 165.9g, content 90%, yield 91%.
Embodiment 10
Into 1500mL reactor add the benzoyl cyanides of 133.8g 98% (1mol), 6.96g ammonium chlorides (0.13mol),
1.6g polyethylene glycol 400s (0.004mol), 246.5ml dimethylbenzene (2mol), it is maintained at 20 DEG C of dropwise addition concentrated sulfuric acids of 544.4g 90%
(5mol) 1 hour, it is warming up to 40 DEG C and is incubated 5 hours；161.7ml methanol (4mol) is added dropwise at 40 DEG C 0.5 hour, is warming up to 90 DEG C
Insulation 0.5 hour, stop reaction, steam methanol.Water 90g is added, separates sour water, 160 grams of water is added into oil reservoir, is washed twice,
Crude product is obtained, rectification under vacuum obtains methyl benzoylformate 167.6g, content 89%, yield 91%.
Claims (10)
1. a kind of new technology of benzoyl cyanide synthesis methyl benzoylformate, it is characterised in that comprise the following steps：
A. benzoyl cyanide is dissolved in organic solvent, adds halide catalyst and phase transfer catalyst, the concentrated sulfuric acid is dripped
Add in system, intermediate imine base sulfate compound is obtained after insulation reaction；
B. methanol is added dropwise in system, methyl benzoylformate is obtained after insulation reaction is complete；
The halide catalyst is the one or more combination in hydrogen chloride, ammonium chloride, sodium chloride, hydrogen bromide or sodium bromide；
The phase transfer catalyst is polyethylene glycol, TBAB, triethyl benzyl ammonia chloride or three normal-butyl myristyl chlorine
Change phosphorus.
2. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：It is described to have
Solvent is toluene, dimethylbenzene or methyl benzoate.
3. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：It is organic molten
The dosage of agent is 0.3~2 times of molar equivalent of benzoyl cyanide.
4. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：Halide
The dosage of catalyst is 0.01~0.13 times of molar equivalent of benzoyl cyanide.
5. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：Phase transfer
The dosage of catalyst is 0.002~0.01 times of molar equivalent of benzoyl cyanide.
6. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：Methanol
Dosage is 0.5~4 times of molar equivalent of benzoyl cyanide.
7. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：The concentrated sulfuric acid
Dosage be benzoyl cyanide 1~5 times of molar equivalent.
8. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：The concentrated sulfuric acid
Concentration be 60%~98%.
9. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：Step a
In the concentrated sulfuric acid is added dropwise in system through 5~60min at 5 DEG C~20 DEG C, during 0.5~5h of insulation reaction is obtained at 20~40 DEG C
Mesosome imido grpup sulfate compound.
10. the new technology of benzoyl cyanide synthesis methyl benzoylformate according to claim 1, it is characterised in that：Step b
In methanol is added dropwise in system through 5~60min at 30~50 DEG C, obtain benzene after 0.5~5h of insulation reaction at 50~100 DEG C
GA methyl esters.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499618A (en) * | 2019-01-17 | 2019-03-22 | 陕西延长石油（集团）有限责任公司 | A kind of catalyst and the preparation method and application thereof being used to prepare benzoyl formic acid and its ester type compound |
| CN109912417A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method |
| CN114478241A (en) * | 2021-12-31 | 2022-05-13 | 山东京博生物科技有限公司 | Preparation method of arylformyl formic ether |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912417A (en) * | 2018-12-29 | 2019-06-21 | 京博农化科技有限公司 | A kind of 2-(2- methylenedioxy phenoxy methyl)-methyl benzoylformate synthetic method |
| CN109499618A (en) * | 2019-01-17 | 2019-03-22 | 陕西延长石油（集团）有限责任公司 | A kind of catalyst and the preparation method and application thereof being used to prepare benzoyl formic acid and its ester type compound |
| CN114478241A (en) * | 2021-12-31 | 2022-05-13 | 山东京博生物科技有限公司 | Preparation method of arylformyl formic ether |
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