CN109400511B - A method of preparing thiourea derivative co-production mercaptopropionic acid - Google Patents
A method of preparing thiourea derivative co-production mercaptopropionic acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
- C07C335/08—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/04—Derivatives of thiourea
- C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
- C07C335/10—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C335/12—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
Abstract
The invention belongs to technical field of organic synthesis, specifically disclose a kind of method for preparing thiourea derivative co-production mercaptopropionic acid, using S- acrylic acid-dithiocarbamate as raw material, neutralized rear aminolysis, obtains thiourea derivative and by-product 3- mercapto propionate in water phase or organic solvent.The acidified obtained 3- mercaptopropionic acid of 3- mercapto propionate.The method that the present invention prepares thiourea derivative co-production mercaptopropionic acid, a practical method is provided for the synthesis of thiourea derivative and 3- mercaptopropionic acid, this method has the characteristics that reaction is mild, the reaction time is short, process flow is simple, thiourea derivative and 3- mercaptopropionic acid high income, with certain industrial economy value.
Description
Technical field
The present invention relates to organic chemical industry fields, and in particular to a kind of work side for preparing thiourea derivative and 3- mercaptopropionic acid
Method.
Background technique
Thiourea derivative is in thiocarbamide molecule NH2- C (=S)-NH2On the basis of, it introduces various groups and replaces H atoms and shape
At compound.Because thiourea derivative contains active atomic sulphur or nitrogen, so that it is floating in agricultural, medicine, organic synthesis, mineral
Choosing, environmental monitoring etc. all have a wide range of applications.
The main method of existing synthesizing thiourea derivative has: isothiocyanic acid ester process, carbon disulfide method and thiocarbonyl transfer
Method etc..(1) isothiocyanic acid ester process prepares isothiocyanate intermediates with rhodanate and halide, then adds with organic amine
At synthesizing thiourea (Reeves WP, Simmons JA, Rudis JA.Phase transfer catalysis preparation
Of aryl thioethers.Synthetic Communications, 1981,11 (10): 781-785.；Lin Q, Fu Y
P, Chen P, et al.Colorimetric chemosensors designed to provide high sensitivity
for Hg2+In aqueous solutions.Dyes and Pigments, 2013,96 (1): 1-6.).Due to the knot of halide
Structure influences its reaction efficiency with rhodanate, only just obtains when prepared by acylthioureas, benzylthiourea and allylthiourea etc.
Good effect.(2) carbon disulfide method, i.e. carbon disulfide and organic amine are Material synthesis thiourea derivative (Allen CFH, Edens
C O, Van Allan J.Ethylenethiourea.Organic Synthesis, 1959,3:394-395；Ballabeni
M, Ballini R, Bigi F, et al.Synthesis ofsymmetrical N, N '-disubstituted thioureas
and heterocyclic thiones from amines andCS2over a ZnO/AL2O3 composite as
Heterogeneous and reusable Catalyst.Journal of Organic Chemistry, 1999,64 (3),
1029-1032).This method is mainly used to synthesis of cyclic thiocarbamide and symmetrical thiocarbamide, but raw material consumption is high.(3) thiocarbonyl shifts
Method, this method by thiocarbonyl transfer reagent and organic amine by necleophilic reaction synthesizing thiourea derivative (Mohanta P K,
Dhar S, Samal S, et al.1- (Methyldithiocarbonyl) imidazole:A useful thiocarbonyl
Transfer reagent for synthesis of substituted thioureas.Tetrahedron, 2000,56
(4): 629-637；Maddani M, Prabhu K R.A convenient method for the synthesis of
Substituted thioureas.Tetrahedron Letters, 2007,48 (40): 7151-7154).This method is used
Thiocarbonyl reagent (such as molybdenum dithiocarbamate) be not easy to be made, and price is higher.
Contain sulfydryl and carboxyl in 3- mercaptopropionic acid molecule simultaneously, is the intermediate of medical fenarol, it can also be used to prepare
Heat stabilizer, curing agent and antioxidant, are a kind of important raw materials of industry, and market prospects are very wide.
Existing 3- mercaptopropionic acid synthetic method mainly has: (1) acrylic acid-hydrogen sulfide high-pressure synthesis method, using hydrogen sulfide as
Sulfhydrylization reagent carries out addition reaction with the acrylic acid with double bond and generates 3- mercaptopropionic acid.The method synthesis technology is simple, but needs
Using the very big hydrogen sulfide of toxicity is raw material, and has by-product 2 mercaptopropionic acid and 3, and 3 '-thio-2 acids generate.(2) sulphur
Sodium hydride method is that nucleophilic addition occurs with acrylonitrile or acrylic acid and synthesizes 3- sulfydryl third using NaHS as sulfhydrylization reagent
Acid method (the synthesis fine-chemical intermediate of Jiang Xu, Chen Jiaxuan, Long Chunmei, Jiang Wenwei β-mercaptopropionic acid, 2004,35
(3): 48-49；Study on the synthesis Qingtao Chemical Engineering College journal of Feng Baicheng β-mercaptopropionic acid, 1998,19 (1): 64-66).(3)
Thiourea-uv Method be thiocarbamide and acrylic acid in presence of hydrochloric acid, generate S- acrylic acid isothiourea, then acted on sodium hydroxide and generate 3-
Mercapto propionate, it is acidified to obtain 3- mercaptopropionic acid；Or Thiourea-uv Method is reacted with a chloropropionic acid, and 3- mercaptopropionic acid is made.(4) sulphur
Sodium thiosulfate method is that sodium thiosulfate and a chloropropionic acid sodium first occur substitution reaction and generates intermediate product, is then decomposed among this
Product obtains 3- mercaptopropionic acid, and (Liu Defu, Wang Mi, Gao Suhua wait .3- chloropropionic acid route to synthesize 3- mercaptopropionic acid chemical industry
With engineering, 2006,23 (2): 130-132；Middle creek wise man youth, the respectful β-メ Le カ ペ ロ ヒ ォ Application acid manufacturing method of high willow
[P] .JP clear 59-29656,1984-09-07).It is not difficult to find that in the synthesis of 3- mercaptopropionic acid or use severe toxicity stink damp
It is easy to produce in body or synthesis process hydrogen sulfide gas (sodium hydrosulfide), or to use a chloropropionic acid or thiocarbamide etc. more expensive
Industrial chemicals, these all limit the industrial production or application of 3- mercaptopropionic acid.
Summary of the invention
The present invention is quasi- to overcome the shortcomings of existing thiourea derivative and 3- mercaptopropionic acid synthetic technology, provides a kind of completely new system
The method of standby thiourea derivative co-production 3- mercaptopropionic acid, to realize that the high-efficiency and economic of thiourea derivative and 3- mercaptopropionic acid closes
At.
The present invention provides a kind of methods for preparing thiourea derivative co-production mercaptopropionic acid, with formula (I) structural formula
S- acrylic acid-dithiocarbamate be raw material, be with chemical formula again after alkali neutralization in water phase or organic solvent
R2NHR3Organic amine carry out aminolysis, obtain have formula (II) shown in structural formula thiourea derivative and 3- mercapto propionate；3- mercapto
The acidified obtained 3- mercaptopropionic acid of base propionate；
Wherein, R1、R2It is independently chosen from C1-C18Alkyl or C3-C18Oxygen-containing alkyl；R3For C1-C18Alkyl, C3-C18's
Oxygen-containing alkyl or hydrogen.
Technical solution of the present invention is reacted with alkali, then again in advance using S- acrylic acid-dithiocarbamate as raw material
Ammonolysis is carried out with the organic amine, separates thiourea derivative and 3- mercaptopropionic acid, the method for the present invention reaction time is short, technique stream
Journey is simple, reacts milder.
The reaction system of alkali and ammonolysis can be water solution system or organic solvent system.
Preferably, the organic solvent is six alkane of dioxy, methanol, ethyl alcohol, tetrahydrofuran, at least one in isopropanol
Kind.
The alkali is preferably at least one of alkali metal hydroxide, carbonate, bicarbonate or ammonium hydroxide；Into
One step is preferably at least one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus or ammonium hydroxide
Kind.
Preferably, the temperature that the S- acrylic acid-dithiocarbamate and alkali of formula (1) react is, for example, 0~30 DEG C.
Preferably, adding organic amine after formula (1) raw material and alkali reaction, carrying out ammonolysis reaction.
Preferably, organic amine (R2NHR3) with S- acrylic acid-dithiocarbamate the mass ratio of the material be 0.9~
1.2。
Preferably, aminolysis reaction temperature is 30-80 DEG C；Preferably 60~70 DEG C.
The ammonolysis reaction time is preferably 2~4 hours.
After ammonolysis reaction, split-phase is extracted, separation obtains thiourea derivative from organic phase；Water phase acidification (acidification pH
Preferably 1~2) isolated 3- mercaptopropionic acid.
R of the present invention1、R2、R3In, the C1-C18Alkyl be preferably C2-C12Alkyl, C6-C12Aryl,
C5-C12Five yuan or hexa-atomic cyclic hydrocarbon radical；Further preferably C2-C8Alkyl, phenyl or benzyl.The C3-C18Contain
The structural formula of oxygen alkyl is, for example ,-R4·O-R5, wherein R4、R5Total carbon number be 3~18.
Preferably, the R1For C2-C12Alkyl, C6-C12Aryl, C5-C12Five yuan or hexa-atomic cyclic hydrocarbon
Base or C4-C15Oxygen-containing alkyl；Preferably C2-C8Alkyl, phenyl, benzyl or C4-C11Oxygen-containing alkyl；Further preferably
Ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, isopentyl, n-hexyl, n-octyl, iso-octyl, ethoxypropyl, the third oxygen third
Base, isopropyl oxygen propyl group, fourth oxygen propyl group or own oxygen propyl group.
Preferably, the R2For C2-C12Alkyl, C6-C12Aryl, C5-C12Five yuan or hexa-atomic cyclic hydrocarbon
Base or C4-C15Oxygen-containing alkyl；Preferably C2-C8Alkyl, phenyl, benzyl or C4-C11Oxygen-containing alkyl；Further preferably
Ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, isopentyl, n-hexyl, n-octyl, iso-octyl, ethoxypropyl, the third oxygen third
Base, isopropyl oxygen propyl group, fourth oxygen propyl group or own oxygen propyl group.
Preferably, R3For C2-C12Alkyl, C6-C12Aryl, C5-C12Five yuan or hexa-atomic cyclic hydrocarbon radical, C4-
C15Oxygen-containing alkyl or hydrogen；Preferably C2-C8Alkyl, phenyl, benzyl, C4-C11Oxygen-containing alkyl or H；Still more preferably
For hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, isopentyl, n-hexyl, n-octyl, iso-octyl, ethoxy
Propyl, the third oxygen propyl group, isopropyl oxygen propyl group, fourth oxygen propyl group or own oxygen propyl group.
Still more preferably, the R3For H.
Preferred preparation method is: at 10~30 DEG C and under stirring, toward the anti-of acrylic acid containing S--dithiocarbamate
Addition NaOH aqueous solution in kettle is answered, after S- acrylic acid-dithiocarbamate solid or organic phase completely disappear, addition has
Machine amine R2NHR3, and stirred 2~4 hours at a temperature of being warming up to 60~70 DEG C.After reaction, liquid separation is stood, thiourea derivative produces
Product are in organic phase.Water phase is added HCl and pH is adjusted to 1~2, and ethyl acetate is then added and is extracted, liquid separation, precipitation are stood
Afterwards, 3- mercaptopropionic acid product is obtained.Wherein preferred S- acrylic acid-dithiocarbamate: NaOH: organic amine: the object of water
The ratio between amount of matter is 1: 1: 1.1: 5~12, and the volume ratio of ethyl acetate and aqueous solution is 1: 1.Preferred desolventizing method is often to subtract
Pressure distillation.
Beneficial effects of the present invention:
In the synthesis of existing 3- mercaptopropionic acid or use severe toxicity hydrogen sulfide gas or synthesis process in be easy generate sulphur
Change hydrogen (sodium hydrosulfide), or to use the more expensive industrial chemicals such as a chloropropionic acid or thiocarbamide.And thiourea derivative
In preparation process or raw material is more expensive or raw material consumption is high, or can only synthesize specific thiourea derivative.
The present invention is quasi- to overcome the shortcomings of existing thiourea derivative and 3- mercaptopropionic acid synthetic technology, provides a kind of completely new system
The method of standby thiourea derivative co-production 3- mercaptopropionic acid, high-efficiency and economic while to realize thiourea derivative and 3- mercaptopropionic acid
Synthesis.Primary raw material S- acrylic acid-dithiocarbamate can be by organic amine, carbon disulfide and acrylic acid through Michael
(Michael) the nearly Atom economy synthesis of addition reaction, by neutralizing, corresponding thiourea derivative and 3- sulfydryl third is made in aminolysis
Acid, process is simple, and reaction is mild, at low cost, and no toxic gas generates, and has and commercially produces potentiality.
Detailed description of the invention
Attached drawing 1 is N- n-propyl-N '-isopropoxide propyl thiocarbamide infrared spectroscopy made from embodiment 1；
Attached drawing 2 is N- isopropoxide propyl-N '-butoxypropyl thiocarbamide infrared spectroscopy made from embodiment 3；
Attached drawing 3 is N- isopropoxide propyl-N '-ethoxycarbonyl propyl thiocarbamide infrared spectroscopy made from embodiment 4；
Attached drawing 4 is N made from embodiment 5, the infrared spectroscopy of N '-dibutoxy propyl thiocarbamide；
Attached drawing 5 is the infrared spectroscopy of 3- mercaptopropionic acid；
Attached drawing 6 is N- n-propyl-N '-isopropoxide propyl thiocarbamide made from embodiment 11H NMR figure；
Specific embodiment
The present invention is further illustrated by following embodiment, but is not restricted by the embodiments.All numbers in embodiment
Quality is unless otherwise specified referred both to percentage.
The preparation of 1 N- n-propyl-N ' of embodiment-isopropoxide propyl thiocarbamide
S- acrylic acid-N- n-propyl the dithiocarbamate that 21.13 parts of purity are 99% is added in reactor, it will
Reactor is added after being dissolved in 22.02 parts of water in 4.07 parts of NaOH, opens stirring, after observing that solid disappears, is warming up to 65 DEG C, then
13.14 parts of isopropoxy propylamine are added, react 2 hours.Reaction terminates, and 19.82 parts of ethyl acetate are added into reactor and fill
Divide stirring, stands liquid separation and obtain upper organic phase and lower layer's water phase, upper organic phase is taken to be evaporated under reduced pressure, obtain N- n-propyl-
(infrared spectroscopy is shown in that Fig. 1, H-NMR figure are shown in 1) Fig. 6, spectral data are shown in Table to N '-isopropoxide propyl thiocarbamide, yield 95.6%.Under
PH is adjusted to 1~2 with HCl by layer water phase, and 19.82 parts of ethyl acetate are then added and are extracted, and liquid separation takes organic phase, and decompression is steamed
Removing ethyl acetate is evaporated, 3- mercaptopropionic acid, yield 94.1% are obtained.
Table 1
The preparation of embodiment 2 N, N '-diη-propyl thiocarbamide
Replace 13.14 parts of isopropoxy propylamine with 6.44 parts of propylamine, with embodiment 1, obtain yield is remaining condition
The 3- mercaptopropionic acid that 96.5%N, N '-diη-propyl thiocarbamide and yield are 93.6%.
The preparation of 3 N- isopropoxide propyl-N ' of embodiment-butoxypropyl thiocarbamide
Reaction is added in the S- acrylic acid-N- isopropoxide propyl dithiocarbamate that 25.18 parts of purity are 99%
In device, 3.79 parts of NaOH are dissolved in after 20.48 parts of water, reactor is added, opened stirring, after observing solution without layering, be warming up to
70 DEG C, 13.69 parts of butoxy propyl amines are then added, react 2.5 hours.Reaction terminates, and 18.43 parts of acetic acid are added into reactor
Ethyl ester is simultaneously sufficiently stirred, and stands liquid separation and obtains upper organic phase and lower layer's water phase, upper organic phase is taken to carry out solvent removal, obtains N-
Isopropoxide propyl-N '-butoxypropyl thiocarbamide (infrared spectroscopy is shown in Fig. 2), yield 94.9%；Lower layer's water phase is with HCl by pH
It is adjusted to 1~2,18.43 parts of ethyl acetate extractions are then added, liquid separation takes organic phase, then is evaporated under reduced pressure removing ethyl acetate, obtains
Obtain 3- mercaptopropionic acid, yield 93.6%.
The preparation of 4 N- isopropoxide propyl-N ' of embodiment-ethoxycarbonyl propyl thiocarbamide
Replace 25.18 parts with the S- acrylic acid-N- ethoxycarbonyl propyl dithiocarbamate that 24.52 parts of purity are 99%
S- acrylic acid-N- isopropoxide propyl dithiocarbamate, 12.57 parts of isopropoxy propylamine replace 13.69 parts of butoxy
It is (red to obtain N- isopropoxide propyl-N '-ethoxycarbonyl propyl thiocarbamide that yield is 94.5% with embodiment 3 for propylamine, remaining condition
External spectrum is shown in Fig. 4) and yield be 92.5% 3- mercaptopropionic acid.
The preparation of embodiment 5 N, N '-dibutoxy propyl thiocarbamide
Reactor is added in the S- acrylic acid-N- butoxypropyl dithiocarbamate that 27.48 parts of purity are 99%
In, 3.93 parts of NaOH are dissolved in after 21.24 parts of water, reactor is added, opened stirring, after observing solution without layering, be warming up to 70
DEG C, 14.20 parts of butoxy propyl amines are then added, react 2 hours.Reaction terminates, and 14.03 parts of n-hexanes are added simultaneously into reactor
It is sufficiently stirred, stands liquid separation and obtain upper organic phase and lower layer's water phase, upper organic phase is evaporated under reduced pressure, and N ,-two fourth of N ' are obtained
Oxygroup propyl thiocarbamide (infrared spectroscopy is shown in Fig. 5), yield 98.5%.Lower layer's water phase HCl tune pH to 1~2, is then added
19.12 parts of ethyl acetate extractions, liquid separation takes organic phase, then is evaporated under reduced pressure removing ethyl acetate, obtains 3- mercaptopropionic acid, yield
It is 95.7%.
The preparation of 6 N- n-propyl-N ' of embodiment-isopropoxide propyl thiocarbamide
S- acrylic acid-N- n-propyl the dithiocarbamate that 22.93 parts of purity are 99% is dissolved in 20.56 parts of dioxies
It is added in reactor after six rings, reactor is added in 4.42 parts of NaOH solids, opens stirring, after observing that solid disappears, heating
To 65 DEG C, 14.26 parts of isopropoxy propylamine are then added, react 3 hours.Reaction terminates, and is evaporated under reduced pressure out dioxane, then
19.91 parts of distilled water are added into reactor and are sufficiently stirred, stand liquid separation, required N- n-propyl-N '-isopropoxide propyl
Thiocarbamide is in organic phase, yield 91.5%.Water phase adds HCl that pH is adjusted to 1~2, and the progress of 17.92 ethyl acetate is then added
Extraction, liquid separation, organic phase are evaporated under reduced pressure removing ethyl acetate again, obtain 3- mercaptopropionic acid, yield 86.1%.
The preparation of 7 N- butoxypropyl-N ', N '-diethyl thiourea of embodiment
Reactor is added in the S- acrylic acid-N- butoxypropyl dithiocarbamate that 29.32 parts of purity are 99%
In, 4.20 parts of NaOH are dissolved in after 22.67 parts of water, reactor is added, opened stirring, after observing solution without layering, be then added
8.44 parts of diethylamine are warming up to 70 DEG C, react 2 hours.Reaction terminates, and 14.96 parts of n-hexanes and abundant are added into reactor
Stirring stands liquid separation and obtains upper organic phase and lower layer's water phase, and upper organic phase is evaporated under reduced pressure, and N- butoxypropyl-is obtained
N ', N '-diethyl thiourea, yield 93.6%.Then 20.41 parts of ethyl acetate are added in lower layer's water phase HCl tune pH to 1~2
Extraction, liquid separation takes organic phase, then is evaporated under reduced pressure removing ethyl acetate, obtains 3- mercaptopropionic acid, yield 87.2%.
The preparation of 8 N- benzyl-N ' of embodiment-ethoxycarbonyl propyl thiocarbamide
S- acrylic acid-N- benzyl the dithiocarbamate that 27.26 parts of purity are 99% is dissolved in 19.85 parts of dioxies six
Be added in reactor after ring, reactors be added in 4.27 parts of NaOH solids, open stirring, after observing that solid disappears, then plus
Enter 12.12 parts of ethoxy propylamines, be warming up to 65 DEG C, reacts 3 hours.Reaction terminates, and is evaporated under reduced pressure out dioxane, then toward anti-
It answers and 19.21 parts of distilled water is added in device and are sufficiently stirred, stand liquid separation, required N- benzyl-N '-ethoxycarbonyl propyl thiocarbamide is having
In machine phase, yield 89.3%.Water phase adds HCl that pH is adjusted to 1~2, and 17.29 ethyl acetate are then added and are extracted, point
Liquid, organic phase are evaporated under reduced pressure removing ethyl acetate again, obtain 3- mercaptopropionic acid, yield 85.1%.
Claims (16)
1. a kind of method for preparing thiourea derivative co-production mercaptopropionic acid, which is characterized in that with the S- with formula (I) structural formula
Acrylic acid-dithiocarbamate be raw material, in water phase or organic solvent after alkali neutralization again with chemical formula be R2NHR3's
Organic amine carries out aminolysis, obtains the thiourea derivative and 3- mercapto propionate with structural formula shown in formula (II)；3- mercaptopropionic acid
The acidified obtained 3- mercaptopropionic acid of salt；
Wherein, R1、R2It is independently chosen from C1-C18Alkyl or C3-C18Oxygen-containing alkyl；R3For C1-C18Alkyl, C3-C18It is oxygen-containing
Alkyl or hydrogen.
2. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that the alkali
For at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus or ammonium hydroxide.
3. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that described has
Solvent is at least one of six alkane of dioxy, methanol, ethyl alcohol, tetrahydrofuran, isopropanol.
4. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that the R1、
R2It is independently chosen from C2-C12Alkyl, C6-C12Aryl, C5-C12Five yuan or hexa-atomic cyclic hydrocarbon radical or C4-C15Oxygen-containing hydrocarbon
Base.
5. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 4, which is characterized in that the R1、
R2It is independently chosen from as C2-C8Alkyl, phenyl, benzyl or C4-C11Oxygen-containing alkyl.
6. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 4, which is characterized in that R1For ethyl,
Propyl, butyl, amyl, n-hexyl, n-octyl, iso-octyl, ethoxypropyl, the third oxygen propyl group, fourth oxygen propyl group or own oxygen propyl group.
7. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 4, which is characterized in that R1For isopropyl
Base, isobutyl group, isopentyl or isopropyl oxygen propyl group.
8. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 4, which is characterized in that R2For ethyl,
Propyl, butyl, amyl, n-hexyl, n-octyl, iso-octyl, ethoxypropyl, the third oxygen propyl group, fourth oxygen propyl group or own oxygen propyl group.
9. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 4, which is characterized in that R2For isopropyl
Base, isobutyl group, isopentyl or isopropyl oxygen propyl group.
10. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that R3For C2-
C12Alkyl, C6-C12Aryl, C5-C12Five yuan or hexa-atomic cyclic hydrocarbon radical, C4-C15Oxygen-containing alkyl or hydrogen.
11. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 10, which is characterized in that R3For C2-
C8Alkyl, phenyl, benzyl, C4-C11Oxygen-containing alkyl or H.
12. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 11, which is characterized in that R3For hydrogen,
Methyl, ethyl, propyl, butyl, amyl, n-hexyl, n-octyl, iso-octyl, ethoxypropyl, the third oxygen propyl group, fourth oxygen propyl group or oneself
Oxygen propyl group.
13. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 11, which is characterized in that R3It is different
Propyl, isobutyl group, isopentyl or isopropyl oxygen propyl group.
14. the method for preparing thiourea derivative co-production mercaptopropionic acid as claimed in claim 12, which is characterized in that R3For H.
15. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that organic amine
It is 0.9~1.5 with S- acrylic acid-dithiocarbamate the mass ratio of the material.
16. the method for preparing thiourea derivative co-production mercaptopropionic acid as described in claim 1, which is characterized in that aminolysis is anti-
Answering temperature is 30-80 DEG C.
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| CN105665148A (en) * | 2016-01-15 | 2016-06-15 | 中南大学 | Isothiocyanate derivative and preparation method and application thereof |
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