CN107118119B - A kind of environmentally friendly synthetic method of cyclopropyl formamide - Google Patents
A kind of environmentally friendly synthetic method of cyclopropyl formamide Download PDFInfo
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- CN107118119B CN107118119B CN201710390640.1A CN201710390640A CN107118119B CN 107118119 B CN107118119 B CN 107118119B CN 201710390640 A CN201710390640 A CN 201710390640A CN 107118119 B CN107118119 B CN 107118119B
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- oxide
- synthetic method
- ammonia
- catalyst
- cyclopropyl formamide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of environmentally friendly synthetic methods of cyclopropyl formamide, and ring first propionic acid is used to react under oxide catalyst with ammonia, so that reaction obtains cyclopropyl formamide.The present invention has many advantages, such as that synthetic route is simple, safety is good, environmental pollution is small, high income.
Description
Technical field
The invention belongs to chemical fields, especially in regard to a kind of environmentally friendly synthetic method of cyclopropyl formamide.
Background technique
There are mainly three types of methods for the synthesis of prior art processes middle ring propyl formamide: the first is original with cyclopropanecarboxylic acid methyl esters
Material carries out aminating reaction with ammonia in autoclave pressure, and cyclopropyl formamide is made；Be for second using cyclopropanecarboxylic acid as raw material, first with
The acylating reagents reaction such as thionyl chloride prepares cyclopropyl formyl chloride, then reacts with ammonia water and prepare cyclopropyl formamide；The third is with ring
Third formic acid and urea pyroreaction prepare cyclopropyl formamide.
First method belongs to pressure reaction, and safety is poor, while using sodium methoxide as alkali, and sodium methoxide is inflammable, and poison
Property is larger, at high cost；There are also quantity of methyl alcohol in production technology is higher, the subsequent process for needing to remove methanol, complex process.
Second method, the acylating reagents such as thionyl chloride are hypertoxic liquid, and high operation requirements easily causes personnel to hurt after leakage
It dies, the management level and safety measure to enterprise propose high request, and the gas generated is that hydrogen chloride, sulfur dioxide etc. are non-
Environmentally friendly gas, it is seriously polluted.
The distillation of the third method high temperature, yield is low, cannot achieve industrialization.
The aftertreatment technology of the prior art is all more complicated simultaneously, and high ammonia-nitrogen wastewater amount is big.It is easier to generate environment
Deleterious effect.
Summary of the invention
That the object of the present invention is to provide a kind of synthetic routes is simple, safety is good, environmental pollution is small, the cyclopropyl first of high income
The environmentally friendly synthetic method of amide.
To reach above-mentioned purpose, the present invention adopts the following technical scheme: a kind of environmentally friendly synthesis of cyclopropyl formamide
Method comprising following steps:
One, ring first propionic acid and catalyst are added in flask, heating；
Two, after being warming up to 140 DEG C, it is passed through ammonia, moisture removal is removed in rectifying, controls fraction temperature at 80~100 DEG C；
Three, continue to heat up, when pot temperature reaches 185 DEG C and fraction temperature is decreased obviously, sampling carries out GC detection,
When detecting that product content conversion ratio reaches 99% or more, stopping is passed through ammonia；
Four, when reaction solution is cooled to 100~110 DEG C, be poured onto cooling bath, after continuing cool to room temperature, cut skin,
Packaging.
Further, the catalyst is magnesia, aluminium oxide, iron oxide, zinc oxide, copper oxide, manganese oxide, oxidation
Cobalt, nickel oxide or more than various oxide compounded catalysts.
Further, the mass ratio of the ring first propionic acid and the catalyst is 1:0.1%~10%.
Compared with prior art, present invention process is simple, is suitble to industrialized production；It is environmentally protective without waste water；High income,
Atom utilization is high；Synthesis under normal pressure, it is highly-safe；The utilization rate of solvent-free reaction, kettle is high, is conducive to production capacity amplification.
Specific embodiment
Technological means used by for the present invention is further explained and the technical effect reached, do in detail with reference to embodiments
It describes in detail bright.
The present invention provides a kind of environmentally friendly synthetic methods of cyclopropyl formamide comprising following steps:
One, ring first propionic acid and catalyst are added in flask, heating；
Two, after being warming up to 140 DEG C, it is passed through ammonia, moisture removal is removed in rectifying, controls fraction temperature at 80~100 DEG C；
Three, continue to heat up, when pot temperature reaches 185 DEG C and fraction temperature is decreased obviously, sampling carries out GC detection,
When detecting that product content conversion ratio reaches 99% or more, stopping is passed through ammonia；
Four, when reaction solution is cooled to 100~110 DEG C, be poured onto cooling bath, after continuing cool to room temperature, cut skin,
Packaging.
Wherein the catalyst in step 1 is magnesia, aluminium oxide, iron oxide, zinc oxide, copper oxide, manganese oxide, oxidation
Cobalt, nickel oxide or more than various oxide compounded catalysts.The mass ratio of the catalyst and the ring first propionic acid simultaneously are as follows:
0.1%~10%:1.
Embodiment one:
The cyclopropanecarboxylic acid of 600g is added in 1L flask, 30g aluminium oxide is added, is warming up to 140 DEG C, is passed through ammonia, rectifying
Moisture content is collected, gradually heating controls fraction temperature at 80-100 DEG C up to 185 DEG C in the process.When temperature reaches 185 DEG C in bottle,
And fraction temperature is decreased obviously, sampling GC detection, product content conversion ratio reaches 99.1%, and stopping is passed through ammonia.Reaction solution drop
It when temperature is to 110 DEG C, is poured onto cooling bath, continues cool to room temperature, be sliced, packaging, weigh to obtain 620g, content 95%, yield
99.5%.
Embodiment two:
The cyclopropanecarboxylic acid of 600g is added in 1L flask, 12g zinc oxide is added, is warming up to 140 DEG C, is passed through ammonia, rectifying
Moisture content is collected, gradually heating controls fraction temperature at 80-100 DEG C up to 185 DEG C in the process.When temperature reaches 185 DEG C in bottle,
And fraction temperature is decreased obviously, sampling GC detection, product content conversion ratio reaches 99.5%, and stopping is passed through ammonia.Reaction solution drop
It when temperature is to 110 DEG C, is poured onto cooling bath, continues cool to room temperature, be sliced, packaging, weigh to obtain 604g, content 97.8%, receives
Rate 99.7%.
Example three:
The cyclopropanecarboxylic acid of 600g is added in 1L flask, 0.3g zinc oxide and 0.3g nickel oxide is added, is warming up to 140 DEG C,
It is passed through ammonia, moisture content is collected in rectifying, and gradually heating controls fraction temperature at 80-100 DEG C up to 185 DEG C in the process.When warm in bottle
Degree reaches 185 DEG C, and fraction temperature is decreased obviously, and sampling GC detection, product content conversion ratio reaches 99.7%, and stopping is passed through ammonia
Gas.It when reaction solution is cooled to 110 DEG C, being poured onto cooling bath, continues cool to room temperature, be sliced, packaging, weigh to obtain 592.6g,
Content 99.6%, yield 99.8%.
Compared with prior art, reaction step of the present invention is few, route is short, process is simple, and raw materials technology is cheap,
It is at low cost, while the later period, without waste water, environmental pollution is small.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (3)
1. a kind of synthetic method of cyclopropyl formamide, it is characterised in that: it includes the following steps:
One, ring first propionic acid and catalyst are added in flask, heating；
Two, after being warming up to 140 DEG C, it is passed through ammonia, moisture removal is removed in rectifying, controls fraction temperature at 80~100 DEG C；
Three, continue to heat up, when pot temperature reaches 185 DEG C and fraction temperature is decreased obviously, sampling carries out GC detection, works as inspection
When measuring product content conversion ratio and reaching 99% or more, stopping is passed through ammonia；
Four, it when reaction solution is cooled to 100~110 DEG C, is poured onto cooling bath, after continuing cool to room temperature, carries out cutting skin, packet
Dress.
2. a kind of synthetic method of cyclopropyl formamide according to claim 1, it is characterised in that: the catalyst is oxidation
Magnesium, aluminium oxide, iron oxide, zinc oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide or more than the catalysis of various oxide Compositional types
Agent.
3. a kind of synthetic method of cyclopropyl formamide according to claim 1, it is characterised in that: the ring first propionic acid and institute
The mass ratio for stating catalyst is 1:0.1%~10%.
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| CN201710390640.1A CN107118119B (en) | 2017-05-27 | 2017-05-27 | A kind of environmentally friendly synthetic method of cyclopropyl formamide |
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| CN201710390640.1A CN107118119B (en) | 2017-05-27 | 2017-05-27 | A kind of environmentally friendly synthetic method of cyclopropyl formamide |
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| CN107118119A CN107118119A (en) | 2017-09-01 |
| CN107118119B true CN107118119B (en) | 2019-08-02 |
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| CN111362822A (en) * | 2020-02-18 | 2020-07-03 | 中国平煤神马能源化工集团有限责任公司 | Preparation method of aromatic amide compound |
Citations (6)
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|---|---|---|---|---|
| EP0780364A1 (en) * | 1995-12-20 | 1997-06-25 | Bayer Ag | Process for the preparation of cyclopropanecarboxylic acid amides |
| US5696270A (en) * | 1989-05-23 | 1997-12-09 | Abbott Laboratories | Intermediate for making retroviral protease inhibiting compounds |
| CN1167480A (en) * | 1994-09-30 | 1997-12-10 | 伊斯曼化学公司 | Processes for the preparation of cyclopropanecarboxylic acid and derivatives thereof |
| CN102249949A (en) * | 2011-05-13 | 2011-11-23 | 奇凯（大连）化工有限公司 | Preparation method of cyclopropyl fenpropathin derivative |
| CN104193645A (en) * | 2014-07-15 | 2014-12-10 | 上海应用技术学院 | Preparation method of chiral dimethyl cyclopropyl carboxamide |
| CN104557356A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Manufacturing method of nitrile and corresponding amine thereof |
-
2017
- 2017-05-27 CN CN201710390640.1A patent/CN107118119B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5696270A (en) * | 1989-05-23 | 1997-12-09 | Abbott Laboratories | Intermediate for making retroviral protease inhibiting compounds |
| CN1167480A (en) * | 1994-09-30 | 1997-12-10 | 伊斯曼化学公司 | Processes for the preparation of cyclopropanecarboxylic acid and derivatives thereof |
| EP0780364A1 (en) * | 1995-12-20 | 1997-06-25 | Bayer Ag | Process for the preparation of cyclopropanecarboxylic acid amides |
| US5739399A (en) * | 1995-12-20 | 1998-04-14 | Bayer Aktiengesellschaft | Process for the preparation of cyclopropanecarboxylic acid amides |
| CN102249949A (en) * | 2011-05-13 | 2011-11-23 | 奇凯（大连）化工有限公司 | Preparation method of cyclopropyl fenpropathin derivative |
| CN104557356A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Manufacturing method of nitrile and corresponding amine thereof |
| CN104193645A (en) * | 2014-07-15 | 2014-12-10 | 上海应用技术学院 | Preparation method of chiral dimethyl cyclopropyl carboxamide |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of cyclopropylamine with phase transfer catalysis;Yi, Jian-ming;《 Journal of Central South University of Technology》;20001231;第7卷(第2期);81-83 |
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