CN1300107C - (2'-thiocyano) ethyl cinnamate compound and its preparing method and use - Google Patents
(2'-thiocyano) ethyl cinnamate compound and its preparing method and use Download PDFInfo
- Publication number
- CN1300107C CN1300107C CNB200510021725XA CN200510021725A CN1300107C CN 1300107 C CN1300107 C CN 1300107C CN B200510021725X A CNB200510021725X A CN B200510021725XA CN 200510021725 A CN200510021725 A CN 200510021725A CN 1300107 C CN1300107 C CN 1300107C
- Authority
- CN
- China
- Prior art keywords
- phenylacrylic acid
- ethyl ester
- thiocyanate
- siccative
- extraction layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention discloses 3-phenylacrylic acid(2-thio cyano)ethyl ester which has the chemical structure. 3-phenylacrylic acid and 2-chloroethanol are used as raw materials for preparing the 3-phenylacrylic acid(2-thio cyano)ethyl ester, and 3-phenylacrylic acid(2-chlorine)ethyl ester of an intermediate body is obtained by esterification reaction; then, the intermediate body and thiocyanate react in a solvent to obtain the 3-phenylacrylic acid(2-thio cyano)ethyl ester. The present invention has the advantages of simple and mature technology, low cost and less waste discharge amount in the preparation process, and provides a clean preparation method. Because the compound provided by the present invention contains thiocyanate which can perform the synergistic effect of bacterium resisting and mildew proofing, compared with cinnamic acid and ethyl cinnamate, the performance of bacterium resisting and mildew proofing is greatly improved, and the present invention can be used as a bateria-resisting and mildew-proofing agent for industrial products in leather, wood, coating material and paper making industry.
Description
One, technical field
The invention belongs to styracin derivative compound and preparing technical field thereof, be specifically related to synthesize the 3-phenylacrylic acid that makes (2 '-thiocyanogen) ethyl ester compound and its production and use with styracin and ethylene chlorhydrin, thiocyanate-.
Two, background technology
The antibacterial and mouldproof of industrial goods is eternal topics, particularly in recent years, along with improving constantly of people's awareness of environment protection and health, to the requirement of the antibiotic and mold proof product that is used for industrial goods also increasingly stringent, the antibacterial and mouldproof compound of high malicious poor efficiency is eliminated gradually.Be example as the mould inhibitor that uses with the leather industry product, commonly used, that contained active principles such as sodium pentachlorophenate, ethyl naphthol, p-NP in the past mould inhibitor, because of toxicity too big, progressively be eliminated or ban use of (Peng Biyu. process hides pre-treatment auxiliary agent-II sanitas and mould inhibitor [J]. leather science and engineering, 1999,9 (3): 53～56.), thereby cause the actual spendable mould inhibitor kind of tannery reducing.Therefore, the new antibacterial and mouldproof compound of efficient, the low toxicity of exploitation, wide spectrum is necessary.
The 3-phenylacrylic acid has another name called styracin, TRANSCINNAMIC ACID and beta-phenyl vinylformic acid, its natural product are present in styracin, Oleum Cinnamomi, the sweet basil wet goods spice berry, it is a kind of important Organic Chemicals, in fields such as food, medicine, agricultural chemicals, daily-use chemical industry, fine chemistry industry, all be widely used (Wang Jiaming. styracin [J]. the Chinese food chemical, 1999, (1): 37～38).Cinnamate derivative then Chang Zuowei synthetic perfume, sun-screening agent etc. is applied to food and daily-use chemical industry industry.In addition, because styracin and ester class thereof all contain α, the beta-unsaturated carbonyl structure, thereby also have anti-microbial property, can be used for the antibiotic of industrial goods.But the anti-microbial property of styracin and ester class thereof is not very high, and is relatively poor to the inhibition effect of microorganism.In order to improve its anti-microbial property, people begin to consider styracin and ester class thereof are carried out chemical modification, as introducing the group that some have anti-microbial effect therein, make it to produce synergy with styracin and ester quasi-molecule thereof, improve their anti-microbial property greatly.As people such as Ning Zhengxiang (Tan Longfei, Ning Zhengxiang. the relation [J] of phenylacrolein, acid compounds structure and anti-microbial activity. the Guangzhou chemistry, 1996, (2): 32～36) just in styracin and ester compound molecule thereof, introduce bromine atoms, synthesized alpha-brominated or α, Beta-bromo styracin and ester compound thereof, their anti-microbial property all is improved greatly.
Three, summary of the invention
The object of the present invention is to provide a kind of is basic structure, the new modification derivative compound with antibacterial and mouldproof effect with the 3-phenylacrylic acid.
It is the method that basic raw material prepares The compounds of this invention with the 3-phenylacrylic acid that another object of the present invention provides a kind of.
The 3rd purpose of the present invention provides above-claimed cpd purposes as the antibacterial mildew inhibitor of industrial goods in leather, timber, coating, paper industry.
Provided by the invention a kind of be that basic structure, the new modification derivative compound with antibacterial and mouldproof effect is that a kind of chemical name is the compound of 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester with the 3-phenylacrylic acid, this compound has the following chemical structure:
This compound can use infrared spectra (IR), carbon-13 nmr spectra (
13CNMR) and mass spectrum (MS) characterize, its data are as follows:
IR(Film)(cm
-1)：
1715.27(s，υ
C＝O)，2156.81(m，υ
as-SCN)
13CNMR(CDCL
3/TMS int)：
166.3321(C＝O)，146.2609(CH(Ar))，
134.0888(Ar(CH))，130.6904(C
meta)，
128.9798(C
ortho)，128.2955(C
para)，
116.8154(CH(CO))，111.6075(SCN)，
62.4557(CH
2(OOC))32.8201(CH
2(SCN))
MSm/e(M
+)：233。
Provided by the invention a kind of be that the method that basic raw material prepares The compounds of this invention is with the 3-phenylacrylic acid; Earlier 3-phenylacrylic acid and ethylene chlorhydrin are carried out esterification, and then introduce thiocyanate ion in the intermediate product molecule, this method may further comprise the steps:
1. be that 1: 4～10: 0.05～0.2 3-phenylacrylic acid, ethylene chlorhydrin and sodium pyrosulfate stirred, are heated under the boiling condition isothermal reaction after 2～10 hours with mol ratio in reaction vessel, distill and reclaim unreacted ethylene chlorhydrin;
2. add the pH regulator agent in the reactant of remainder, making pH value of reactants is 7.5～8.0, uses organic extractant extractive reaction thing again, and wash the organic extraction layer with water, making its pH value is 6.0～7.0, adds siccative then and remove moisture in the organic extraction layer, and remove by filter siccative;
3. the organic extraction layer is changed in the water distilling apparatus, organic extractant is also reclaimed in distillation, must have 3-phenylacrylic acid (2 '-chlorine) the pure product of ethyl ester of following structure after the residual material underpressure distillation:
These pure product characterize with infrared spectra (IR), and data are as follows:
IR(Film)(cm
-1)：
1716.04(s，υ
C＝O)，1637.64，1578.37，1496.62，1450.73(υ
Ar-H)；
4. be 1: 1～1: 5 3-phenylacrylic acid (2 '-chlorine) ethyl ester, thiocyanate-with mol ratio and be that 1: 5～1: 10 solvent stirs in reaction vessel, heats with 3-phenylacrylic acid (2 '-chlorine) ethyl ester mol ratio, in isothermal reaction under the boiling condition after 2～12 hours, distill and reclaim unreacted solvent;
5. use organic extractant extractive reaction thing, and wash organic extraction layer at least 2 times with water, in the organic extraction layer, add siccative then and remove moisture, and remove by filter siccative;
6. the organic extraction layer is changed in the water distilling apparatus, organic extractant is also reclaimed in distillation, residuals after underpressure distillation 3-phenylacrylic acid (2 '-thiocyanogen) the pure product of ethyl ester.
Wherein used thiocyanate-is any in potassium sulfocyanate, Sodium Thiocyanate 99 or the ammonium thiocyanate.Used solvent is any in ethanol, methyl alcohol, Virahol, acetone, methylacetone or the Methyl isobutyl ketone.Used pH regulator agent is any in yellow soda ash, sodium bicarbonate, salt of wormwood, sodium hydroxide or the potassium hydroxide.Used siccative is any in anhydrous magnesium sulfate, anhydrous sodium sulphate or the anhydrous sodium carbonate.Used organic extractant is any in ether, methylene dichloride, the chloroform.
Compound of the present invention can use by the antibacterial mildew inhibitor as industrial goods in leather, timber, coating, paper industry.
The present invention has the following advantages:
1, the thiocyanate ion that contains in (2 '-thiocyanogen) ethyl ester compound because 3-phenylacrylic acid provided by the invention, produced the synergy of antibacterial and mouldproof with the 3-phenylacrylic acid, thereby in the antibacterial test of much common bacterium, mould, compare with ethyl cinnamate with styracin without the inventive method modification, its required minimum inhibitory concentration will be hanged down several times (test data sees Table 1), this shows that compound through modification provided by the invention has not only improved the antibacterial and mouldproof performance greatly, but also has increased a new kind for antibiotic mold proof product.
2, (2 '-thiocyanogen) ethyl ester compound is to be feedstock production with cheap styracin, chloroethanol and thiocyanate-etc. because 3-phenylacrylic acid provided by the invention, thereby product cost is cheaper.
3, preparation method's operational condition provided by the invention is simple, technical maturity, enforcement that can be fairly large.
4, owing to the most of reagent that adopts among the preparation method provided by the invention can reclaim, and utilize once more, therefore, the waste discharge amount in the preparation process is few, is a kind of synthetic method that meets the cleaning of environmental protection requirement.
5,3-phenylacrylic acid provided by the invention (2 '-thiocyanogen) ethyl ester compound use range is extensive, can use by the antibacterial mildew inhibitor as industrial goods in leather, timber, coating, paper industry.
Four, embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
1, getting 3-phenylacrylic acid 60g (0.4mol), ethylene chlorhydrin 135ml (2.0mol) and sodium pyrosulfate 4.8g (0.04mol) adds in the 500ml round-bottomed flask, stir, be heated to boiling, behind isothermal reaction backflow 4h, distill and reclaim unreacted ethylene chlorhydrin; Then, adding concentration is 10% aqueous sodium carbonate in the reactant of remainder, and making pH value of reactants is 6.0, uses 200ml extracted with diethyl ether reactant again, and washes ether layer with water, and making its pH value is 6.0; Again to ether layer in add anhydrous sodium carbonate 50g, remove moisture, leave standstill 3h, and remove by filter yellow soda ash thereafter; Ether layer is changed in the water distilling apparatus, and ether is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 120 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-chlorine) ethyl ester product 72.0g after the underpressure distillation, and productive rate is 85.5%.
2, get 3-phenylacrylic acid (2 '-chlorine) ethyl ester 30g (0.14mol), acetone 51.60ml (0.7mol) and potassium sulfocyanate 13.61g (0.14mol) add together in the 500ml round-bottomed flask stir, heating, behind isothermal reaction backflow 2h under the boiling condition, distill and reclaim unreacted acetone; And then with methylene dichloride 100ml extractive reaction thing, and wash dichloromethane layer with water 3 times, and in dichloromethane layer, add anhydrous magnesium sulfate 50g then and remove moisture, leave standstill 3h, and remove by filter sal epsom; Dichloromethane layer is changed in the water distilling apparatus, and methylene dichloride is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 150 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester product 28.12g after the underpressure distillation, and productive rate is 86.2%.
Embodiment 2
1, getting 3-phenylacrylic acid 60g (0.4mol), ethylene chlorhydrin 243ml (3.6mol) and sodium pyrosulfate 2.4g (0.02mol) adds in the 500ml round-bottomed flask, stir, be heated to boiling, behind isothermal reaction backflow 8h, distill and reclaim unreacted ethylene chlorhydrin; Then, adding concentration is 10% sodium bicarbonate aqueous solution in the reactant of remainder, and making pH value of reactants is 8.0, uses 300ml dichloromethane extraction reactant again, and washes dichloromethane layer with water, and making its pH value is 6.5; Again to dichloromethane layer in add anhydrous magnesium sulfate 50g, remove moisture, leave standstill 3h, and remove by filter sal epsom thereafter; Dichloromethane layer is changed in the water distilling apparatus, and methylene dichloride is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 120 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-chlorine) ethyl ester product 70.0g after the underpressure distillation, and productive rate is 83.1%.
2, get 3-phenylacrylic acid (2 '-chlorine) ethyl ester 30g (0.14mol), Virahol 85.7ml (1.12mol) and Sodium Thiocyanate 99 45.4g (0.56mol) add together in the 500ml round-bottomed flask stir, heating, behind isothermal reaction backflow 10h under the boiling condition, distill and reclaim unreacted Virahol; And then with ether 160ml extractive reaction thing, and wash ether layer with water 3 times, and in ether layer, add anhydrous magnesium sulfate 55g then and remove moisture, leave standstill 4h, and remove by filter sal epsom; Ether layer is changed in the water distilling apparatus, and ether is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 150 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester product 30.72g after the underpressure distillation, and productive rate is 94.2%.
Embodiment 3
1, getting 3-phenylacrylic acid 60g (0.4mol), ethylene chlorhydrin 189ml (2.8mol) and sodium pyrosulfate 3.84g (0.032mol) adds in the 500ml round-bottomed flask, stir, be heated to boiling, behind isothermal reaction backflow 6h, distill and reclaim unreacted ethylene chlorhydrin; Then, adding concentration is 10% wet chemical in the reactant of remainder, and making pH value of reactants is 7.5, uses 250ml chloroform extraction reactant again, and washes chloroform layer with water, and making its pH value is 7.0; Again to chloroform layer in add anhydrous sodium sulphate 50g, remove moisture, leave standstill 3h, and remove by filter sodium sulfate thereafter; Chloroform layer is changed in the water distilling apparatus, and chloroform is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 120 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-chlorine) ethyl ester product 73.6g after the underpressure distillation, and productive rate is 87.4%.
2, get 3-phenylacrylic acid (2 '-chlorine) ethyl ester 30g (0.14mol), ethanol 50.0ml (0.84mol) and Sodium Thiocyanate 99 22.7g (0.28mol) add together in the 500ml round-bottomed flask stir, heating, behind isothermal reaction backflow 5h under the boiling condition, distill and reclaim unreacted ethanol; And then with methylene dichloride 120ml extractive reaction thing, and wash dichloromethane layer with water 2 times, and in dichloromethane layer, add anhydrous sodium carbonate 60g then and remove moisture, leave standstill 2h, and remove by filter yellow soda ash; Dichloromethane layer is changed in the water distilling apparatus, and methylene dichloride is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 150 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester product 27.56g after the underpressure distillation, and productive rate is 84.5%.
Embodiment 4
1, getting 3-phenylacrylic acid 60g (0.4mol), ethylene chlorhydrin 108ml (1.6mol) and sodium pyrosulfate 7.2g (0.06mol) adds in the 500ml round-bottomed flask, stir, be heated to boiling, behind isothermal reaction backflow 7h, distill and reclaim unreacted ethylene chlorhydrin; Then, adding concentration is 5% aqueous sodium hydroxide solution in the reactant of remainder, and making pH value of reactants is 8.0, uses 200ml extracted with diethyl ether reactant again, and washes ether layer with water, and making its pH value is 6.0; Again to ether layer in add anhydrous sodium carbonate 50g, remove moisture, leave standstill 3h, and remove by filter yellow soda ash thereafter; Ether layer is changed in the water distilling apparatus, and ether is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 120 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-chlorine) ethyl ester product 69.2g after the underpressure distillation, and productive rate is 82.2%.
2, get 3-phenylacrylic acid (2 '-chlorine) ethyl ester 30g (0.14mol), methyl alcohol 39.6ml (0.98mol) and ammonium thiocyanate 31.97g (0.42mol) add together in the 500ml round-bottomed flask stir, heating, behind isothermal reaction backflow 8h under the boiling condition, distillation is also reclaimed unreacted methanol; And then with chloroform 140ml extractive reaction thing, and wash chloroform layer with water 4 times, and in chloroform layer, add anhydrous sodium sulphate 70g then and remove moisture, leave standstill 6h, and remove by filter sodium sulfate; Chloroform layer is changed in the water distilling apparatus, and chloroform is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 150 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester product 25.63g after the underpressure distillation, and productive rate is 78.6%.
Embodiment 5
1, getting 3-phenylacrylic acid 60g (0.4mol), ethylene chlorhydrin 270ml (4.0mol) and sodium pyrosulfate 9.6g (0.08mol) adds in the 500ml round-bottomed flask, stir, be heated to boiling, behind isothermal reaction backflow 2h, distill and reclaim unreacted ethylene chlorhydrin; Then, adding concentration is 5% potassium hydroxide aqueous solution in the reactant of remainder, and making pH value of reactants is 7.5, uses 300ml dichloromethane extraction reactant again, and washes dichloromethane layer with water, and making its pH value is 6.5; Again to dichloromethane layer in add anhydrous magnesium sulfate 50g, remove moisture, leave standstill 3h, and remove by filter sal epsom thereafter; Dichloromethane layer is changed in the water distilling apparatus, and methylene dichloride is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 120 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-chlorine) ethyl ester product 71.5g after the underpressure distillation, and productive rate is 85.0%.
2, get 3-phenylacrylic acid (2 '-chlorine) ethyl ester 30g (0.14mol), methylacetone 122ml (1.4mol) and Sodium Thiocyanate 99 56.8g (0.7mol) add together in the 500ml round-bottomed flask stir, heating, behind isothermal reaction backflow 12h under the boiling condition, distill and reclaim unreacted methylacetone; And then with methylene dichloride 180ml extractive reaction thing, and wash dichloromethane layer with water 5 times, and in dichloromethane layer, add anhydrous sodium sulphate 80g then and remove moisture, leave standstill 4h, and remove by filter sodium sulfate; Dichloromethane layer is changed in the water distilling apparatus, and methylene dichloride is also reclaimed in distillation, and residual material is at pressure 0.095MPa, under 150 ℃ of the temperature, obtains 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester product 28.74g after the underpressure distillation, and productive rate is 88.1%.
In order to investigate the effect that 3-phenylacrylic acid provided by the invention (2 '-thiocyanogen) ethyl ester uses as antibacterial mildew inhibitor, the present invention has carried out the test of the minimum inhibitory concentration (MIC) of following several bacteriums and mould to styracin, ethyl cinnamate and 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester simultaneously.Minimum inhibitory concentration is the minimal inhibitory concentration of instigating the microorganism growth impaired development required.Minimum inhibitory concentration is more little, illustrates that compound is strong more to the inhibition effect of this microorganism, and the antibacterial and mouldproof performance is good more.The test of minimum inhibitory concentration (MIC) according to a conventional method (Lv Jia manger. light industry product mildew-resistant technology [M]. Beijing: Chemical Industry Press, 2003) carry out, culture condition is: culturing bacterium is 37 ℃, mould is 28 ℃, relative humidity is all greater than 90%, the incubation time of bacterium is 2 days, and the incubation time of mould is 7 days.Test result sees Table 1.
Table 1 minimum inhibitory concentration (unit: mg/kg)
| Styracin | Ethyl cinnamate | The 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester | |
| Escherichia coli and staphylococcus aureus aspergillus niger aspergillus flavus aspergillus oryzae fusarium Trichoderma viride bread mold Chaetomium globosum Penicillium citrinum | 600 500 250 250 250 300 400 500 500 250 | 500 450 250 250 250 250 400 500 400 250 | 30 30 60 60 60 30 60 90 120 30 |
In addition, also ethyl ester is as leather fungicide with the 3-phenylacrylic acid that obtained (2 '-thiocyanogen) in the present invention, and the mildew-resistant that has been used for wet blue leather is handled, and detailed process is as follows:
Add the 100kg normal-temperature water in the rotary drum that the 100kg wet blue leather is housed, add 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester then, making its mass percent concentration is 0.5%, rotates after 2 hours, go out bulging, deposit.Take out a wet blue leather at random and carry out fungicidal properties test, and compare with the wet blue leather of handling through styracin and ethyl cinnamate.Testing method adopts moist chamber suspension method (Chen Yiben, Ou Yangyousheng, Huang Xiaorong etc. industrial bactericide [M]. Beijing: Chemical Industry Press, 2001), test strain comprises the mixing mould of aspergillus niger, flavus, Penicillium citrinum, bread mould, viride and Chaetomium globosum.Is 28 ℃ for the examination wet blue leather in temperature, and relative humidity is all greater than after cultivating 28 days in 90% the incubator, carries out the mildew-resistant ranking according to the growing state of mould on the leather, the results are shown in Table 2.
Table 2
| Styracin | Ethyl cinnamate | The 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester | |
| The mildew-resistant grade | 4 | 4 | 1 |
Annotate: the mildew spot is about 1mm on 1 grade of expression leather, and it is sparse to distribute:
4 grades the expression leathers on mildew spot major part more than 5mm or whole surface be covered with mycelia.
Claims (10)
1, a kind of chemical name is the compound of 3-phenylacrylic acid (2 '-thiocyanogen) ethyl ester, and this compound has the following chemical structure:
2, the preparation method of the described compound of a kind of claim 1, this method may further comprise the steps:
1. be that 1: 4～10: 0.05～0.2 3-phenylacrylic acid, ethylene chlorhydrin and sodium pyrosulfate stirred, are heated under the boiling condition isothermal reaction after 2～10 hours with mol ratio in reaction vessel, distill and reclaim unreacted ethylene chlorhydrin;
2. add the pH regulator agent in the reactant of remainder, making pH value of reactants is 7.5～8.0, uses organic extractant extractive reaction thing again, and wash the organic extraction layer with water, making its pH value is 6.0～7.0, adds siccative then and remove moisture in the organic extraction layer, and remove by filter siccative;
3. the organic extraction layer is changed in the water distilling apparatus, organic extractant is also reclaimed in distillation, after the residual material underpressure distillation 3-phenylacrylic acid (2 '-chlorine) the pure product of ethyl ester;
4. be 1: 1～1: 5 3-phenylacrylic acid (2 '-chlorine) ethyl ester, thiocyanate-with mol ratio and be that 1: 5～1: 10 solvent stirs in reaction vessel, heats with 3-phenylacrylic acid (2 '-chlorine) ethyl ester mol ratio, in isothermal reaction under the boiling condition after 2～12 hours, distill and reclaim unreacted solvent;
5. use organic extractant extractive reaction thing, and wash organic extraction layer at least 2 times with water, in the organic extraction layer, add siccative then and remove moisture, and remove by filter siccative;
6. the organic extraction layer is changed in the water distilling apparatus, organic extractant is also reclaimed in distillation, residuals after underpressure distillation 3-phenylacrylic acid (2 '-thiocyanogen) the pure product of ethyl ester.
3, preparation method according to claim 2 is characterized in that used thiocyanate-is any in potassium sulfocyanate, Sodium Thiocyanate 99 or the ammonium thiocyanate.
4,, it is characterized in that used solvent is any in ethanol, methyl alcohol, Virahol, acetone, methylacetone or the Methyl isobutyl ketone according to claim 2 or 3 described preparation methods.
5,, it is characterized in that used pH regulator agent is any in yellow soda ash, sodium bicarbonate, salt of wormwood, sodium hydroxide or the potassium hydroxide according to claim 2 or 3 described preparation methods.
6, preparation method according to claim 4 is characterized in that used pH regulator agent is any in yellow soda ash, sodium bicarbonate, salt of wormwood, sodium hydroxide or the potassium hydroxide.
7,, it is characterized in that used siccative is any in anhydrous magnesium sulfate, anhydrous sodium sulphate or the anhydrous sodium carbonate according to claim 2 or 3 described preparation methods.
8, preparation method according to claim 6 is characterized in that used siccative is any in anhydrous magnesium sulfate, anhydrous sodium sulphate or the anhydrous sodium carbonate.
9,, it is characterized in that used organic extractant is any in ether, methylene dichloride, the chloroform according to claim 2 or 3 described preparation methods.
10, the compound in the claim 1 in leather industry as the application of the antibacterial mildew inhibitor of industrial goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021725XA CN1300107C (en) | 2005-09-23 | 2005-09-23 | (2'-thiocyano) ethyl cinnamate compound and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021725XA CN1300107C (en) | 2005-09-23 | 2005-09-23 | (2'-thiocyano) ethyl cinnamate compound and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749246A CN1749246A (en) | 2006-03-22 |
| CN1300107C true CN1300107C (en) | 2007-02-14 |
Family
ID=36604922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510021725XA Expired - Fee Related CN1300107C (en) | 2005-09-23 | 2005-09-23 | (2'-thiocyano) ethyl cinnamate compound and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300107C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913178A (en) * | 2021-10-13 | 2022-01-11 | 深圳市添金利新材料科技有限公司 | Novel pigment based on light discoloration and preparation method thereof |
-
2005
- 2005-09-23 CN CNB200510021725XA patent/CN1300107C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1749246A (en) | 2006-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1300107C (en) | (2'-thiocyano) ethyl cinnamate compound and its preparing method and use | |
| CN1151245A (en) | Synergistic antimicrobial composition of 1,2-dibromo-2,4-dicyanobutane and esters of parahydroxybenzoic acid | |
| CN1019977C (en) | Process for preparing metal complex of N-methyl-11-aza-10-deoxy-10-dihydroerythromycins A and 11-aza-10-deoxy-10-dihydroerythromycins A | |
| CN1030470C (en) | Preparation method for new antibiotic aureonuclemycin and agricultural bactericide | |
| CN1732157A (en) | 1-alkyl-3-aminoindazoles | |
| CN1903830A (en) | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol | |
| EP0048585A1 (en) | Antibiotics TM-531 B and TM-531 C | |
| CN1069115C (en) | Mecerized fabrics and additives and production thereof | |
| CN1775791A (en) | New method for preparing 2-deoxy-D-glucose | |
| CN1537833A (en) | Soluble silicon potassium fertilizer | |
| CN1807752A (en) | Surface modification method for slow-release type anti-insect and anti-microbe fabric | |
| CN101037421A (en) | 4-(2-Benzothiazolyl aminoiminomethyl) phenoxyacetic acid and cupric complexes and preparation methods thereof | |
| CN109535065B (en) | Longifolenyl quaternary ammonium salt compound and synthesis method and application thereof | |
| CN1234672C (en) | Process for producing alpha-asarone raw material | |
| CN1174681C (en) | Changchuan mycin agricultural bactericide and its preparing method and use | |
| CN108752399B (en) | Synthesis method of isopropyl-beta-D-thiogalactoside | |
| CN102344397A (en) | Method for purifying valnemulin hydrochloride | |
| CN101066944A (en) | Synthesis process of sulcoatrione | |
| US4703128A (en) | Guanidylfungin derivatives and their production | |
| CN1651407A (en) | Sodium alkyl acyl acetaldehyde sulfite, its synthesis method and use | |
| CN1319446C (en) | Technique for producing novel bio-agricultural chemical songgang-mycin | |
| CN1944427A (en) | Novel macro-molecular compound, its preparing method and use | |
| JPS61192298A (en) | Production of erythromycin d | |
| CN1284459C (en) | Sterilization algae removal anti-fungus agent and preparation method thereof | |
| CN1126764C (en) | Oligomeric conjak-glucomannan-propyl disulfur aldehydate, and its preparing process and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |