CN105175286B - A kind of preparation method of hydrochloric acid alkyl guanidine salt - Google Patents
A kind of preparation method of hydrochloric acid alkyl guanidine salt Download PDFInfo
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- CN105175286B CN105175286B CN201510504185.4A CN201510504185A CN105175286B CN 105175286 B CN105175286 B CN 105175286B CN 201510504185 A CN201510504185 A CN 201510504185A CN 105175286 B CN105175286 B CN 105175286B
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Abstract
The invention discloses one kind using alkyl amine aqueous solution as reaction raw materials, it is passed through hydrogen chloride gas (including the hydrogen chloride emission produced in Chemical Manufacture) and carries out acidification reaction, add phenols or quinones stabilizer and carry out addition reaction with the cyanamide aqueous solution, the hydrochloric acid alkyl guanidine salt product shown in formula I, reaction equation are obtained through decompression dehydration：R in formula1For CH3Or C2H5；R2For H, CH3Or C2H5, the present invention, which utilizes the hydrogen chloride emission produced in Chemical Manufacture to be passed through in alkyl amine aqueous solution, is used for the synthesis of hydrochloric acid alkyl guanidine salt, not only greatly reduces the production cost of hydrochloric acid alkyl guanidine salt, also eliminates due to the environmental pollution that the presence of excessive hydrochloric acid is caused.And phenols or quinones stabilizer are added in the synthetic reaction of hydrochloric acid alkyl guanidine salt, the stability of alkyl guanidine and cyanamide is added well, the decomposition of alkyl guanidine and the polymerization of cyanamide are restrained effectively, side reaction is reduced, reaction yield and hydrochloric acid alkyl guanidine salt quality is improved.
Description
Technical field
The present invention relates to a kind of preparation method of hydrochloric acid alkyl guanidine salt.
Background technology
Hydrochloric acid alkyl guanidine salt outward appearance is white solid, is very important pesticide intermediate, its chemical structure of general formula is as follows：
For example：R1And R2For CH3Hydrochloride guanidinesalt be that insecticide wards off aphid mist (Pirimicarb) and bactericide diformazan is phonetic
The key intermediate of phenol (Dimethirimol)；R1And R2For C2H5Hydrochloric acid diethyl guanidinesalt be insecticide pirimiphos-methyl
(Pirimiphos-methyl) key intermediate；R1It is C2H5、R2The second guanidinesalt of hydrochloric acid one for being H is bactericide ethirimol
(Ethirimol) or bupirimate (Bupirimate) key intermediate.
The purity and yield of hydrochloric acid alkyl guanidine salt directly influence the production cost and product quality of product downstream.At present
The preparation method of hydrochloric acid alkyl guanidine salt mainly has S- methyl isothioureas method and cyanamide method.
S- methyl isothiourea methods are with corresponding alkylamine to prepare hydrochloric acid by raw material of S- methyl isothioureas hydrochloride
Alkyl guanidine salt, reaction yield and product content are higher, but this method can generate foul gas methyl mercaptan, and production environment is severe.
Cyanamide method is using dicyandiamide or cyanamide as Material synthesis hydrochloric acid alkyl guanidine salt：
First, synthesized by initiation material of dicyandiamide
Document (E.A.Werner, J.Bell, J.Chem.Soc., Trans., 1922,121,1790-1794) report with
Dicyandiamide and dimethylamine hydrochloride are pyroreaction 3 hour synthetic hydrochloric acid diformazan guanidinesalt of the raw material at 180 DEG C；Document
(RO51039,1968-5-22) reports similar synthetic method, i.e., melt dicyandiamide and amine hydrochlorate more than mixed material
Synthetic hydrochloric acid guanidinesalt is reacted under the reaction temperature of 20~30 DEG C of point, such as using dicyandiamide and dimethylamine hydrochloride as raw material, toluene is
Solvent, back flow reaction 4~5 hours, with 80% yield, 99.5% content synthetic hydrochloric acid diformazan guanidinesalt.
Dicyandiamide is temperature is more than 80 DEG C and has and easily decomposes in the presence of water, using dicyandiamide method synthetic hydrochloric acid diformazan guanidinesalt pair
Moisture asks higher, further, since the alkylamine hydrochloride easily moisture absorption, therefore, harsh using this method synthesis condition, it is difficult to realize
Industrialization.Only obtained it is noted that document (GB1272499A, 1970-12-15) carries out checking test to dicyandiamide method
A small amount of hydrochloric acid alkyl guanidine salt product, while some substantial amounts of accessory substances are generated, such as hydrochloric acid substitution biguanides.
2nd, synthesized by initiation material of cyanamide
Synthesis material cyanamide is main to be existed with the aqueous solution or crystallization sterling, and its chemical property is extremely active, it is easy to
Generation Binary Aggregation generates dicyandiamide, and hydrolyzes the materials such as generation urea, hardly possible production, storage and transport.
The cyanamide aqueous solution or melting cyanamide are added dropwise to temperature by document (GB1272499A, 1970-12-15) report
In 200 DEG C or so of alkylamine hydrochloride, by 83~95% yield (in terms of cyanamide), 89~98.5% content synthesis salt
Dialkylaminobenzoic acid guanidinesalt.
This method is only when the concentration of cyanamide is bigger and the temperature of reaction is higher, and the content and yield of products obtained therefrom are just got over
It is high., it is necessary to reduce the generation of side reaction by high temperature evaporating water in time when using cyanamide reactant aqueous solution, but
Part cyanamide can be caused to be lost with vapor, and industrial operation difficulty is big.Reacted when using the melting cyanamide of high concentration
When, although product yield and content are better than using the cyanamide aqueous solution, but the bigger cyanamide of concentration, production, storage and transport
Difficulty it is bigger, cost is higher.
The content of the invention
The purpose of the present invention is to overcome above-mentioned existing technological deficiency there is provided the hydrochloric acid alkyl guanidine salt shown in a kind of formula I
Preparation method,
R in formula I1For CH3Or C2H5；R2For H, CH3Or C2H5。
The reaction equation of compound is as follows shown in formula I：
The present invention is, using the alkyl amine aqueous solution shown in formula II as reaction raw materials, to be passed through hydrogen chloride gas and be acidified, acid
Change and stabilizer is added after reaction, then addition reaction is carried out with the cyanamide aqueous solution, addition reaction is finished obtains formula I through decompression dehydration
Shown hydrochloric acid alkyl guanidine salt.
Hydrogen chloride gas of the present invention includes the hydrogen chloride emission produced in Chemical Manufacture.
Stabilizer of the present invention includes phenols or quinones, preferably hydroquinones, 4- tert-butyl catechols, 2-
One kind in TBHQ, benzoquinones, tetrachloroquinone.
The molar ratio of alkylamine of the present invention and hydrogen chloride and cyanamide is Wan Ji An ︰ Lvization Qing ︰ cyanamides
The ︰ 1 of=1.15 ︰ 1.02, the mass percentage concentration of alkyl amine aqueous solution is 40%, and the mass percentage concentration of the cyanamide aqueous solution is
50%；The consumption of stabilizer is the 0.1%~0.5% of cyanamide aqueous solution quality；Acidification reaction temperature is 20 DEG C~30 DEG C, acid
Change 2~3 hours reaction time, addition reaction temperature is 40 DEG C~80 DEG C, and 4~5 hours addition reaction time, reaction is finished, and is subtracted
Press-dehydrating obtains hydrochloric acid alkyl guanidine salt product.Product yield ＞ 90% (in terms of cyanamide), content ＞ 95%.
The present invention concrete operation step be：
The aqueous solution of alkylamine is added in reactor, hydrogen chloride gas is passed through while stirring in less than 15 DEG C, is controlled
Be passed through speed, led within about 1 hour or so, continue 20 DEG C~30 DEG C insulation 2 hours after, add stabilizer, and be warming up to 40 DEG C~
80 DEG C are at the uniform velocity added dropwise the cyanamide aqueous solution, are incubated 1 hour after dripping off within 4 hours, reaction is finished, and decompression dehydration obtains the depicted of formula I
White solid product hydrochloric acid alkyl guanidine salt.
The present invention is passed through generation alkylamine hydrochloric acid in alkyl amine aqueous solution using the hydrogen chloride emission produced in Chemical Manufacture
Saline solution is used for the synthesis of hydrochloric acid alkyl guanidine salt, not only greatly reduces the production cost of hydrochloric acid alkyl guanidine salt, also eliminates
The environmental pollution caused due to the presence of excessive hydrochloric acid.First alkylamine is formed because the present invention uses alkylamine with hydrogen chloride
Hydrochloride, excessive alkylamine and cyanamide addition generate alkyl guanidine, and the alkalescence of alkyl guanidine is better than alkylamine, and alkyl guanidine can be with
Alkylamine hydrochloride reaction generation hydrochloric acid alkyl guanidine salt, discharges alkylamine and continues subsequent reactions.Due to reaction intermediate alkyl
Guanidine is unstable, is easily decomposed into urea and Ammonia material, influences the yield and content of product：
Therefore, the present invention is stable by adding phenols or quinones in the synthetic reaction (addition reaction) in hydrochloric acid alkyl guanidine salt
Agent, adds the stability of alkyl guanidine and cyanamide well, restrained effectively the decomposition of alkyl guanidine and the polymerization of cyanamide,
So as to reduce side reaction, while improving the quality of reaction yield and hydrochloric acid alkyl guanidine salt.
Embodiment
In order to further appreciate that the present invention, the present invention is further illustrated with reference to specific embodiment.(following % refers both to matter
Percentage is measured, the yield of hydrochloric acid alkyl guanidine salt is in terms of cyanamide, and hydrogen chloride is that the hydrogen chloride produced in Chemical Manufacture is useless
Gas.)
Embodiment 1：The synthesis of hydrochloride guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) 40% dimethylamine agueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.084g hydroquinones, and be warming up to 60
DEG C, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 hour has been reacted
Finish, decompression dehydration obtains 116.7g white solids, content 95.5%, yield 90.6%.
Embodiment 2：The synthesis of hydrochloride guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) 40% dimethylamine agueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.42g 2- TBHQs, and
40 DEG C are warming up to, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 is small
When, reaction is finished, and decompression dehydration obtains 116.9g white solids, content 95.1%, yield 90.4%.
Embodiment 3：The synthesis of hydrochloride guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) 40% dimethylamine agueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.25g 4- tert-butyl catechols, and
60 DEG C are warming up to, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 is small
When, reaction is finished, and decompression dehydration obtains 117.7g white solids, content 95.4%, yield 91.3%.
Embodiment 4：The synthesis of hydrochloride guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) 40% dimethylamine agueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.25g benzoquinones, and is warming up to 60 DEG C, in 4
Or so hour at the uniform velocity instills 84g (1.0mol) the 50% cyanamide aqueous solution, and drop finishes, insulation reaction 1 hour, and reaction is finished, and is subtracted
Press-dehydrating obtains 116.8g white solids, content 95.6%, yield 90.8%.
Embodiment 5：The synthesis of hydrochloride guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) 40% dimethylamine agueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.42g tetrachloroquinones, and be warming up to 80
DEG C, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 hour has been reacted
Finish, decompression dehydration obtains 117.5g white solids, content 95.3%, yield 91.0%.
Embodiment 6：The synthesis of hydrochloric acid diethyl guanidinesalt
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
209.9g (1.15mol) 40% diethylamine aqueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.25g 4- tert-butyl catechols, and
60 DEG C are warming up to, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 is small
When, reaction is finished, and decompression dehydration obtains 143.6g white solids, content 95.6%, yield 90.9%.
Embodiment 7：The synthesis of the second guanidinesalt of hydrochloric acid one
In tri- mouthfuls of reaction bulbs of 500ml equipped with mechanical agitation, thermometer, reflux condenser and dropping funel, add
129.4g (1.15mol) the 40% monoethyl amine aqueous solution, starts stirring, is cooled to less than 15 DEG C, has at the uniform velocity led in 1 hour or so
37.2g (1.02mol) hydrogen chloride, after 20 DEG C~30 DEG C of continuation insulation 2 hours, adds 0.42g 4- tert-butyl catechols, and
80 DEG C are warming up to, 84g (1.0mol) the 50% cyanamide aqueous solution was at the uniform velocity instilled in 4 hours or so, drop finishes, and insulation reaction 1 is small
When, reaction is finished, and decompression dehydration obtains 116.3g white solids, content 95.4%, yield 90.2%.
Claims (2)
1. a kind of preparation method of hydrochloric acid alkyl guanidine salt, it is characterised in that：It is former by reaction of the alkyl amine aqueous solution shown in formula II
Material, is passed through hydrogen chloride gas and is acidified, and alkylamine is excessive；Stabilizer is added after acidification reaction, then is entered with the cyanamide aqueous solution
Row addition reaction, addition reaction is finished obtains hydrochloric acid alkyl guanidine salt product shown in formula I through decompression dehydration,
Reaction equation is：
R in formula1For CH3Or C2H5；R2For H, CH3Or C2H5,
The stabilizer is in hydroquinones, 4- tert-butyl catechols, 2- TBHQs, benzoquinones, tetrachloroquinone
It is a kind of；
The ︰ 1 of molar ratio=1.15 ︰ 1.02 of alkane base amine ︰ chlorine hydrogen ︰ cyanamides, the mass percentage concentration of alkyl amine aqueous solution
For 40%, the mass percentage concentration of the cyanamide aqueous solution is 50%；The consumption of stabilizer is the 0.1% of cyanamide aqueous solution quality
~0.5%；Acidification reaction temperature is 20 DEG C~30 DEG C, and 2~3 hours acidification reaction time, addition reaction temperature is 40 DEG C~80
DEG C, 4~5 hours addition reaction time.
2. the preparation method of hydrochloric acid alkyl guanidine salt according to claim 1, it is characterised in that described hydrogen chloride gas bag
Include the hydrogen chloride emission produced in Chemical Manufacture.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1272499A (en) * | 1970-02-09 | 1972-04-26 | Sueddeutsche Kalkstickstoff | Process for the production of alkyl guanidine and n,n-dialkylguanidine hydrochlorides |
| US5489709A (en) * | 1992-03-20 | 1996-02-06 | Cambridge Neuroscience, Inc. | Preparation of substituted guanidines |
| CN101528821A (en) * | 2006-10-23 | 2009-09-09 | Ppg工业俄亥俄公司 | Primer composition and articles incorporating the primer |
| CN102516130A (en) * | 2011-11-26 | 2012-06-27 | 赤峰万泽制药有限责任公司 | Preparation method of metformin hydrochloride |
-
2015
- 2015-08-17 CN CN201510504185.4A patent/CN105175286B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1272499A (en) * | 1970-02-09 | 1972-04-26 | Sueddeutsche Kalkstickstoff | Process for the production of alkyl guanidine and n,n-dialkylguanidine hydrochlorides |
| US5489709A (en) * | 1992-03-20 | 1996-02-06 | Cambridge Neuroscience, Inc. | Preparation of substituted guanidines |
| CN101528821A (en) * | 2006-10-23 | 2009-09-09 | Ppg工业俄亥俄公司 | Primer composition and articles incorporating the primer |
| CN102516130A (en) * | 2011-11-26 | 2012-06-27 | 赤峰万泽制药有限责任公司 | Preparation method of metformin hydrochloride |
Non-Patent Citations (1)
| Title |
|---|
| "氨基氰稳定剂的选择";朱福印等;《无机盐工业》;20090228;第41卷(第2期);摘要，第2部分 * |
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