CN109942463A - A kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- - Google Patents
A kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- Download PDFInfo
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- CN109942463A CN109942463A CN201910338985.1A CN201910338985A CN109942463A CN 109942463 A CN109942463 A CN 109942463A CN 201910338985 A CN201910338985 A CN 201910338985A CN 109942463 A CN109942463 A CN 109942463A
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Abstract
The present invention relates to the synthetic methods of bis- [3- (dimethylamino) propyl] ureas of 1,3- of one kind, comprising: step 1 takes urea and N, and N- dimethyl -1,3- propane diamine is mixed in a certain proportion, and protection reagent is added, is warming up to 105-150 DEG C of reaction；Protective agent is selected from one of hydrazine or hydrazine derivate or a variety of；Step 2 removes unreacted N, obtains mesh after N- dimethyl -1,3- propane diamine and wants bis- [3- (dimethylamino) propyl] ureas of product 1,3-.A possibility that protection reagent of the invention slowly resolves into the ammonia with reproducibility in the case where reacting heating condition, protects reaction product, reduces product oxidation.Synthetic method of the invention without nitrogen protection, without being further purified or refinery decolorization can directly obtain colourless product, product can also directly be used as the raw material further reacted.Method of the invention requires reaction condition the production cost that low, equipment is simple, can significantly reduce target compound, is suitable for a small amount of and mass production 1, bis- [3- (dimethylamino) propyl] ureas of 3-.
Description
Technical field
The present invention relates to the production technical field of urea derivative, specifically a kind of 1,3- is bis- [3- (dimethylamino) propyl]
The synthetic method of urea.
Background technique
1,3- bis- [3- (dimethylamino) propyl] ureas are the chemical substances that two amino of urea is replaced by amine, are to have
Such as the molecule of flowering structure:
1,3- bis- [3- (dimethylamino) propyl] ureas are widely used, can be used for medicine, pesticide, dyestuff, electroplating intermediate,
The industries such as petrochemical industry, semiconductors manufacture and macromolecule are a kind of important fine organic chemical industry's intermediates.For example, 1,3- is bis-
[3- (dimethylamino) propyl] urea can be used for synthesizing polyquaternium, be widely used in daily use chemicals, weaving, medicine, water process and plating
Equal fields, can be used as high performance Biocidal algae-killing agent, adhesive mud remover, electroplating additive, can be used as in hair washing product excellent
Conditioner, can be used as moisturizer in skin face cream, can be used as antistatic agent, antidusting agent and moisturizer in textile product,
As mordant etc. in inkjet printing.
Currently, the general synthetic method of 1,3- bis- [3- (dimethylamino) propyl] ureas, is the N by urea and proper proportion,
After the mixing of N- dimethyl -1,3- propane diamine, heating reaction in an inert atmosphere.Since reaction temperature is higher, raw material amine and product
Have the possibility of oxidation, the product caused have color even color it is deeper, and high impurity content influence product quality and
Yield.For the generation for reducing oxidation reaction, usually reacted under conditions of nitrogen protection.However it is experimentally confirmed that nitrogen is protected
The effect of shield is usually not fully up to expectations, logical with bis- [3- (dimethylamino) propyl] ureas of 1,3- of nitrogen protection production on the market at present
Chang Douyou color.Other reducing agents are added to be protected, more impurity may be introduced, and improve cost.Therefore, it finds and closes
Suitable protective agent, not only needs efficient protecting effect, also requires not introduce impurity as far as possible, and few improve is produced into as far as possible
This.
The method of purification of bis- [3- (dimethylamino) propyl] ureas of 1,3- is documented, is under high vacuum after completion of the reaction
Product is distilled out, the coloration of the product obtained in this way is fine.The disadvantage of this method is 1,3- bis- [3- (dimethylamino)
Propyl] urea boiling point it is very high, vacuum distillation needs vacuum level requirements to be achieved high.In this way, both having increased technique wants summation device
Condition, and cost is substantially increased, while limiting production capacity.Therefore, this method is generally unsuitable for the bis- [3- of large-scale 1,3-
(dimethylamino) propyl] urea preparation.
Summary of the invention
For technological gap in the prior art, the present invention provides 1,3- of one kind conjunction of bis- [3- (dimethylamino) propyl] ureas
At method, the synthetic method is low to reaction condition requirement, equipment is simple, will not introduce impurity, and target product is high-quality, is suitable for
A small amount of and bis- [3- (dimethylamino) propyl] ureas of mass production 1,3-.
The present invention is achieved by the following technical solutions:
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- of one kind, includes the following steps:
Step 1 takes urea and N, and N- dimethyl -1,3- propane diamine is mixed in a certain proportion, and protection reagent is added, is warming up to
105-150 DEG C of reaction；The protective agent is selected from one of hydrazine or hydrazine derivate or a variety of；
Step 2 removes unreacted N, obtains mesh after N- dimethyl -1,3- propane diamine and wants the bis- [3- (dimethylamine of product 1,3-
Base) propyl] urea.
Further, the specific method is as follows for the reaction of the step 1: take urea and N, N- dimethyl -1,3- propane diamine with
Certain proportion mixing is added protection reagent, is warming up to 105-115 DEG C, is gradually warming up to 130 DEG C after reacting 5-10min, keeps
It is warming up to 150 DEG C after 0.5-1.5h, cooling after 1h is kept to stop reaction.
Further, the dosage of the protection reagent is the 0.1%~30% of urea quality.
Further, the urea and N, the molar ratio of N- dimethyl -1,3- propane diamine are 1:(1.8-2.5).
Further, the hydrazine derivate is selected from semicarbazides or carbohydrazide.
Further, the protection reagent is the reagent comprising hydrazine or hydrazine derivate.
Further, the protective agent selected from hydrazine hydrate, hydrazonium salt, the hydrate of hydrazine derivate, hydrazine derivate salt in
At least one.
For synthetic method of the invention with urea and N, N- dimethyl -1,3- propane diamine is that raw material produces the bis- [3- (diformazans of 1,3-
Amido) propyl] urea, hydrazine or hydrazine derivative are added in reaction process as protection reagent, item of the protection reagent in reaction heating
The ammonia with reproducibility is slowly resolved under part, is played a protective role to product, thus a possibility that reducing product oxidation；Together
When, when protection reagent is hydrochloric acid amido urea, semicarbazide hydrochloride can also decompose generation urea, this is one of raw material, therefore will not give
Reaction system brings new impurity into.Therefore, compared with prior art, the advantages of the present invention are as follows:
Synthetic method of the invention without in an inert atmosphere heating reaction, therefore to reaction condition require it is low, equipment is simple
It is single；Protect reagent protecting effect good, it is easy to use and efficient, low coloration or colourless high quality target product can be synthesized, is produced
Object can also be directly used as the raw material further reacted, and will not usually introduce impurity influential on product quality；This hair
Bright method can significantly reduce the production cost of target compound, be suitable for a small amount of and mass production 1, the bis- [3- (dimethylamine of 3-
Base) propyl] urea.
Figure of description
Fig. 1 is the gas chromatogram of the target product of embodiment 1.
Specific embodiment
Applicant is in conjunction with specific embodiments described in further details technical solution of the present invention below, so that this field
Technical staff may be better understood the present invention and can be practiced, but range is claimed not as the present invention in illustrated embodiment
Restriction.
Embodiment 1
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 4.38g is taken, N, N- dimethyl -1,3- propane diamine 18.6g mixing are added 85% hydrazine hydrate of 0.5g, are warming up to
105-110 DEG C, 130 DEG C are gradually warming up to after reacting 5-10min, 150 DEG C is warming up to after keeping 1h, is cooled to 30 after keeping 1h
℃.Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent thick liquid product, with urine
Plain collecting rate is 92.6%.
The target product of the present embodiment is subjected to gas chromatographic analysis, while with from the limited public affairs of the triumphant chemistry science and technology of one hundred generation of Shanghai
Bis- [3- (dimethylamino) propyl] ureas of 1,3- of department's purchase are that standard items are compareed.Under identical gas phase condition, standard items
Appearance time is 1.337min, and the target product appearance time of the present embodiment is 1.332min.The present embodiment target product gas phase
Chromatography purity is greater than 98%.
Embodiment 2
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 11.7g is taken, 0.3g semicarbazide hydrochloride and 0.1g is added in N, N- dimethyl -1,3- propane diamine 38.7g mixing
85% hydrazine hydrate is warming up to 110 DEG C or so, is gradually warming up to 130 DEG C after reacting 5-10min, is warming up to 150 DEG C after keeping 1h,
30 DEG C are cooled to after keeping 1h.Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent glue
Thick liquid product.With urea collecting rate for 93.4%.Product detects the product of the chloride salt form containing 1.1% through liquid phase,
It can be directly used for the synthesis of polyquaternium.
Embodiment 3
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 17.0g is taken, N, N- dimethyl -1,3- propane diamine 66.84g mixing are added 0.3g carbohydrazide, are warming up to 110
DEG C or so, 130 DEG C are gradually warming up to after reacting 5-10min, 150 DEG C is warming up to after keeping 1h, cools down after keeping 1h.Vacuum distillation
Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent thick liquid product, is with urea collecting rate
94.0%.The present embodiment target product gas chromatographic analysis purity is greater than 98%.
Embodiment 4
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 63.2g is taken, 1.2g semicarbazide hydrochloride and 0.3g is added in N, N- dimethyl -1,3- propane diamine 269g mixing
50% hydrazine hydrate is warming up to 110-115 DEG C, is gradually warming up to 130 DEG C after reacting 5-10min, is warming up to 150 DEG C after keeping 1h,
Cool down after keeping 1h.Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent thick liquid
Product, with urea collecting rate for 94.8%.The present embodiment target product gas chromatographic analysis purity is greater than 98%.
Embodiment 5
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 120.0g is taken, N, N- dimethyl -1,3- propane diamine 496.3g mixing are added 85% hydrazine hydrate of 0.12g, rise
Temperature is gradually warming up to 130 DEG C after reacting 5-10min to 110 DEG C or so, is warming up to 150 DEG C after keeping 1h, cools down after keeping 1h.
Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent thick liquid product, with ureometer
Yield is 94.0%.The present embodiment target product gas chromatographic analysis purity is greater than 98%.
Embodiment 6
The synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- is as follows in the present embodiment:
Urea 35.0g is taken, N, N- dimethyl -1,3- propane diamine 132.4g mixing are added 10.5g carbohydrazide, are warming up to 110
DEG C or so, 130 DEG C are gradually warming up to after reacting 5-10min, 150 DEG C is warming up to after keeping 1h, cools down after keeping 1h.Vacuum distillation
Unreacted N is steamed, N- dimethyl -1,3- propane diamine obtains colorless and transparent thick liquid product, is with urea collecting rate
93.8%.The present embodiment target product gas chromatographic analysis purity is greater than 98%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. one kind 1, the synthetic method of bis- [3- (dimethylamino) propyl] ureas of 3-, which comprises the steps of:
Step 1 takes urea and N, and N- dimethyl -1,3- propane diamine is mixed in a certain proportion, and protection reagent is added, is warming up to 105-
150 DEG C of reactions；The protective agent is selected from one of hydrazine or hydrazine derivate or a variety of；
Step 2 removes unreacted N, obtains mesh after N- dimethyl -1,3- propane diamine and wants the bis- [3- (dimethylamino) of product 1,3-
Propyl] urea.
2. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 1, which is characterized in that
The specific method is as follows for the reaction of the step 1: taking urea and N, N- dimethyl -1,3- propane diamine is mixed in a certain proportion, and is added
Reagent is protected, is warming up to 105-115 DEG C, 130 DEG C is gradually warming up to after reacting 5-10min, is warming up to 150 after keeping 0.5-1.5h
DEG C, keep cooling after 1h to stop reaction.
3. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 1, which is characterized in that
The dosage of the protection reagent is the 0.1%~30% of urea quality.
4. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 1, which is characterized in that
The urea and N, the molar ratio of N- dimethyl -1,3- propane diamine are 1:(1.8-2.5).
5. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 1, which is characterized in that
The hydrazine derivate is selected from semicarbazides or carbohydrazide.
6. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 1, which is characterized in that
The protection reagent is the reagent comprising hydrazine or hydrazine derivate.
7. a kind of synthetic method of bis- [3- (dimethylamino) propyl] ureas of 1,3- according to claim 6, which is characterized in that
The protective agent is selected from least one of hydrazine hydrate, hydrazonium salt, the hydrate of hydrazine derivate, the salt of hydrazine derivate.
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| US4157388A (en) * | 1977-06-23 | 1979-06-05 | The Miranol Chemical Company, Inc. | Hair and fabric conditioning compositions containing polymeric ionenes |
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