CN109020855A - A kind of method of the halogenated -1- thiocyanate groups vinyl compound of ultrasonic-assisted synthesis Z-2- - Google Patents
A kind of method of the halogenated -1- thiocyanate groups vinyl compound of ultrasonic-assisted synthesis Z-2- Download PDFInfo
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- CN109020855A CN109020855A CN201810808892.6A CN201810808892A CN109020855A CN 109020855 A CN109020855 A CN 109020855A CN 201810808892 A CN201810808892 A CN 201810808892A CN 109020855 A CN109020855 A CN 109020855A
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- Prior art keywords
- halogenated
- vinyl compound
- thiocyanate groups
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Links
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 34
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 33
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 16
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000002585 base Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- -1 vinyl compound Chemical class 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000010907 mechanical stirring Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 42
- 238000013019 agitation Methods 0.000 description 21
- 239000000376 reactant Substances 0.000 description 17
- 239000002024 ethyl acetate extract Substances 0.000 description 15
- BPVHWNVBBDHIQU-UHFFFAOYSA-N 2-bromoethynylbenzene Chemical group BrC#CC1=CC=CC=C1 BPVHWNVBBDHIQU-UHFFFAOYSA-N 0.000 description 13
- 238000004587 chromatography analysis Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- RUEKPBLTWGFBOD-UHFFFAOYSA-N bromoethyne Chemical group BrC#C RUEKPBLTWGFBOD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000006886 vinylation reaction Methods 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- GDWZLADUGAKASM-UHFFFAOYSA-N 2-chloroethynylbenzene Chemical group ClC#CC1=CC=CC=C1 GDWZLADUGAKASM-UHFFFAOYSA-N 0.000 description 1
- VOHWEKIUKSUIDT-UHFFFAOYSA-N 2-iodoethynylbenzene Chemical group IC#CC1=CC=CC=C1 VOHWEKIUKSUIDT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010490 three component reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
- C07C331/04—Thiocyanates having sulfur atoms of thiocyanate groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of the halogenated -1- thiocyanate groups vinyl compound of ultrasonic-assisted synthesis Z-2-.Under ultrasonic wave and mechanical stirring synergistic effect, three component selective addition reactions occur for the halogenated alkynes of azochlorosulfonate acid ion liquid catalyst 1-, potassium rhodanide and water, efficiently synthesize the halogenated -1- thiocyanate groups vinyl compound of Z-2- under condition of no solvent.This method raw material is easy to get, and reaction condition simplicity, mild, green energy conservation, reaction selectivity and yield are high, substrate functional group excellent compatibility, application value with higher.
Description
Technical field
The invention belongs to organic compounds to synthesize field, and in particular to a kind of halogenated alkynes, potassium rhodanide and water addition are closed
At the method for the halogenated -1- thiocyanate groups vinyl compound of Z-2-.
Background technique
Halogenated -1- thiocyanate groups the vinyl compound of Z-2- is a kind of very important polyfunctional compound, is had non-
Often important physiological activity.But since the active function groups of the compound are more, synthetic method is very limited.Document report at present
The direct synthesis method of the halogenated -1- thiocyanate groups vinyl compound of the Z-2- in road only has South China Science & Engineering University Jiang Huanfeng professor and exists
The patent of invention (application number CN201610579617.2) of application in 2017 and its paper delivered
(Adv.Synth.Catal.2017,359,1208).This method are as follows: under 100 DEG C of hot conditions, silver acetate catalyst 1- halogen
It is reacted in acetum 3 hours for alkynes with the potassium rhodanide of 2 times of chemical moles, generates the halogenated -1- thiocyanates of Z-2-
Base vinyl compound target product.
But this method has the following disadvantages
1) in synthesis Z-2- chloro -1- thiocyanate groups vinyl compound and Z-2- iodo -1- thiocyanate groups vinylation
Yield is very low when closing object；
2) use of transition-metal catalyst leads to potential transition metal residue problem in the final product；
3) under hot conditions, acid flux material can not only cause certain corrosion to consersion unit, also to alkynes substrate function
Group's tolerance generates certain detrimental effect.
Summary of the invention
In order to overcome deficiency present in traditional technology, the purpose of the present invention is be intended to provide a kind of not only can be improved instead
Efficiency is answered, production cost is reduced, the halogenated -1- thiocyanate groups second of environmental-friendly Z-2- of reaction three waste discharge can also be reduced
The preparation method of ene compound.
In order to achieve the above technical purposes, the present invention provides a kind of halogenated -1- thiocyanic acids of ultrasonic-assisted synthesis Z-2-
The method of ester group vinyl compound exists the halogenated alkynes of 1-, rhodanate, water and azochlorosulfonate acid ion liquid with 1 structural formula of formula
Addition reaction is carried out under ultrasound and stirring condition, the halogenated -1- thiocyanate groups ethylene chemical combination of Z-2- of structural formula described in formula 2 is made
Object；
R is the alkyl or substituted hydrocarbon radical of C1~C30；X is Cl, Br or I.
Preparation method of the present invention, using the halogenated alkynes of 1-, rhodanate, water as reaction substrate, azochlorosulfonate acid ion liquid
For catalyst, three components are carried out under ultrasonic wave and stirring cooperation condition and are reacted, the halogenated -1- thiocyanate groups vinylation of Z-2- is obtained
Close object.The present inventor innovatively has found, under the catalysis of the ionic liquid, cooperates the ultrasonic wave and mechanical stirring
Double mechanism under, the yield of product and the configuration preference of product can be obviously improved, moreover, can be also obviously shortened
Preparation time.In addition, azochlorosulfonate acid ion liquid catalyst can be recycled at least 5 times, and catalytic performance is not after by extraction product
Become.Preparation method of the present invention, whole preparation process realizes solvent free, and reaction condition is mild, substrate functional group compatibility
It is excellent, application value with higher.
R be alkyl, five yuan~seven yuan of naphthenic base, the cyclic hydrocarbon radical of unsaturated five yuan~seven yuan of part, benzene, five yuan~
Hexa-member heterocycle aryl or by least two aromatic rings in phenyl ring, five-ring heterocycles, hexa-member heterocycle and close the condensed ring radical of formation
Group.
Preferably, R C1~C30Alkyl；C5~C30Five yuan of naphthenic base；C6~C30Hexa-atomic naphthenic base；C7
~C30Seven yuan of naphthenic base；C5~C30Unsaturated five yuan of the cyclic hydrocarbon radical in part, C6~C30Part it is unsaturated hexa-atomic
Cyclic hydrocarbon radical or C7~C30Unsaturated seven yuan of the cyclic hydrocarbon radical in part；Benzene；C5~C30Five-ring heterocycles aryl；C6~C30Six
Circle heterocyclic ring aryl；Or by least two aromatic rings in the phenyl ring, five-ring heterocycles, hexa-member heterocycle and close the condensed ring of formation
Group.
The alkyl, naphthenic base, cyclic hydrocarbon radical benzene, heterocyclic aryl, condensed ring group ring structure on allow containing substituted
Base；The substituent group is preferably H, C1~C6 alkyl, the alkoxy of C1~C6, hydroxyl, sulfydryl, methyl mercapto, fluoroform sulphur
Base, cyano, acyl group, C2~C30Ester group, trifluoromethyl, halogen or cyano.
Preferred scheme, the halogenated alkynes of 1- include 1- halogenated aryl acetylene, 1- haloheteroaryl acetylene and 1- halogenated
Alkyl acetylene.
The halogenated alkynes of the 1- has at least one of formula 1-A, the compound of structural formula of formula 1-B or formula 1-C；
R1~R7It is alone H, C1~C10Alkyl, C1~C10Alkyl oxygroup, C6~C20Aryl, C5~C20Heterocycle
Aryl, hydroxyl, sulfydryl, methyl mercapto, trifluoromethylthio, cyano, acyl group, C2~C30Ester group, trifluoromethyl, halogen or cyano；
Or R1~R5In, adjacent group constitutes some or all of 5~10 yuan unsaturated cyclic structures together；Institute
Also allow in the cyclic structure stated containing hetero atom and substituent group；
Y is O, S, CH2Or NH.
Further preferably, R1~R7It is alone H, C1~C10Alkyl, C1~C10Alkyl oxy, hydroxyl, sulfydryl, first sulphur
Base, trifluoromethylthio, cyano, acyl group, C2~C30Ester group, trifluoromethyl, halogen or cyano.
Preferably, the rhodanate is the alkali metal salt or ammonium salt of thiocyanate radical；Further preferably thiocyanic acid
At least one of sodium, potassium rhodanide, ammonium thiocyanate.
Most preferably, the rhodanate is potassium rhodanide.The study found that the yield of the cis-product of potassium rhodanide is more
It is high.
Preferably, theoretical molar amount of the dosage of rhodanate not less than reaction, it is preferable that rhodanate, 1- halogen
It is not less than 1, preferably 1~2: 1 for the molar ratio of alkynes；Further preferably 1.1~1.2: 1.Preferably add under ratio, it is suitable
The yield of formula anomeric product is further promoted.
As preferred: theoretical molar amount of the dosage of water not less than reaction, it is preferable that mole of the halogenated alkynes of water, 1-
Than being not less than 1, preferably 1~2: 1；Further preferably 1: 1.
The azochlorosulfonate acid ion liquid is with trifluoro methylsulfonimide (NTf-) for anion part, and cationic portion has
Sulfonic ionic liquid.
Preferably, the azochlorosulfonate acid ion liquid is at least one of the compound with structure described in formula 3；
R8For the alkyl of C1~C3；The integer that n is 1~4.
Preferably, the R8For methyl；N is 3~4.Preferred azochlorosulfonate acid ion liquid, structural formula are formula 3-A:
Preferably, the molar ratio of the halogenated alkynes of 1-, azochlorosulfonate acid ion liquid is 1: 0.1-0.3；Preferably 1: 0.1.
It is 20W, preferably 25~60W, most preferably 30W that the power of ultrasound, which is not less than,.
Supersonic frequency is not less than 15KHz；Preferably 17KHz~80KHz；Further preferably 17KHz~60KHz, more into
One step is preferably 17KHz.
Under preferred ultrasonic power and frequency, the yield of cis-product is higher.
The discovery that the present invention also innovates, under the ultrasonic wave added, cooperative mechanical stirring can shorten the reaction time
Under the premise of, it can also surprisingly promote conversion ratio.
The present invention innovatively has found, in three component reaction process, carries out ultrasound and mechanical stirring to reaction system, has
Obvious synergy can be obviously shortened the reaction time, promote the yield of product.
Preferably, the speed of agitator is preferably 300~750r/min.
Addition reaction is without additional heating, in the progress under room temperature, it is preferable that the temperature of addition reaction
It is 25~50 DEG C.
Preferably, the addition reaction time is 15~35 minutes.
By taking the halogenated phenylacetylene of 1- as an example, reaction route (square formula 1) is as follows:
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) azochlorosulfonate acid ion liquid catalyst is easily recycled, cheap；
2) solvent-free reaction, post-processing is simple, and reaction cost is low；
3) reaction condition is mild, and functional group compatibility is good；
4) alkynes of bromo, chloro or iodo can obtain highly selective and high receipts using addition method of the invention
Rate；
5) it is combined using ultrasonic wave and mechanical stirring, while shortening the reaction time, improves reaction yield；
6) reaction efficiency is high, and no other organic by-products generate, and sterling can be obtained in vacuum drying after extraction.
Specific embodiment
Following specific embodiments are intended to further illustrate the content of present invention, rather than limit the protection of the claims in the present invention
Range.
Embodiment 1
The preparation of Z-2- bromo -1- thiocyanate groups styrene:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid 3-A (18.3mg), gained mixed liquor are anti-in ultrasonic agitation (500 revs/min) reaction unit of 30W/17KHz
It answers 15 minutes.Ethyl acetate extracts reactant, vacuum drying Z-2- bromo -1- thiocyanate groups styrene 224mg, yield
96%.
Embodiment 2:
With the ultrasonic agitation of the ultrasonic agitation replacement 30W/17KHz of 50W/40KHz:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg) sulphur
Acid ion liquid 3-A (18.3mg), gained mixed liquor react in ultrasonic agitation (500 revs/min) reaction unit of 50W/40KHz
15 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is 87%.
Embodiment 3:
With the ultrasonic agitation of the ultrasonic agitation replacement 35W/17KHz of 20W/17KHz:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid 3-A (18.3mg), gained mixed liquor are anti-in ultrasonic agitation (500 revs/min) reaction unit of 20W/17KHz
It answers 30 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is
78%.
Embodiment 4:
With the ultrasonic agitation of the ultrasonic agitation replacement 30W/17KHz of 30W/40KHz:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid 3-A (18.3mg), gained mixed liquor are anti-in ultrasonic agitation (500 revs/min) reaction unit of 30W/40KHz
It answers 15 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z- bromo -1- thiocyanate groups styrene yield is 75%.
Embodiment 5:
The potassium rhodanide of 1.2 moles is replaced with the potassium rhodanide of 1.0 moles
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (97mg), water (18mg), sulphur
Acid ion liquid 3-A (18.3mg), gained mixed liquor react in ultrasonic agitation (500 revs/min) reaction unit of 30W/17KHz
15 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is 80%.
Embodiment 6
Potassium rhodanide is replaced with sodium sulfocyanate
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), sodium sulfocyanate (81mg), water (18mg), sulphur
Acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor is in ultrasonic agitation (500 revs/min) reaction unit of 30W/17KHz
Reaction 15 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is
84%.
Embodiment 7
Potassium rhodanide is replaced with ammonium thiocyanate
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), ammonium thiocyanate (76mg), water (18mg), sulphur
Acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor is in ultrasonic agitation (500 revs/min) reaction unit of 30W/17KHz
Reaction 15 minutes.Ethyl acetate extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is
77%.
Embodiment 8
Azochlorosulfonate acid ion liquid catalyst circulation experiment:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (905mg), potassium rhodanide (580mg), water (90mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (91.5mg), ultrasonic agitation (500 revs/min) reaction unit of gained mixed liquor in 30W/17KHz
Middle reaction 20 minutes.After ethyl acetate extracts reactant, continue that same amount of phenyl bromoacetylene is added into azochlorosulfonate acid ion liquid,
Potassium rhodanide and water, gained mixed liquor react under the same conditions.Circulation carries out 4 times.Liquid-phase chromatographic analysis Z-2- bromo -1- sulphur
Cyanic acid ester group styrene yield is followed successively by 97%, 96%, 96%, 94%, 93%.
Embodiment 9:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (in formula 3, R8For methyl, n 2) (17.5mg), ultrasonic agitation (500 of the gained mixed liquor in 30W/17KHz
Rev/min) react 15 minutes in reaction unit.Ethyl acetate extracts reactant, liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanates
Base styrene yield is 44%.
Comparative example 1:
Replacement ultrasonic wave stirring assisted reaction (being only stirred) is stirred to react with room temperature (30 DEG C):
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor are stirred at room temperature (500 revs/min) and react 15 minutes.Acetic acid second
Ester extracts reactant, and liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is 17%.
Comparative example 2:
Replacement ultrasonic wave stirring assisted reaction (being only stirred) is stirred to react with 60 DEG C:
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor are stirred to react 15 minutes at 60 DEG C.Ethyl acetate extraction reaction
Object, liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield are 24%.
Comparative example 3:
With single ultrasonic response condition replacement ultrasonic wave stirring concerted reaction condition (being only ultrasonically treated):
It in 10mL round-bottomed flask, sequentially adds phenyl bromoacetylene (181mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), ultrasonic reaction 15 minutes in 30W/17KHz of gained mixed liquor.Ethyl acetate extraction
Reactant is taken, liquid-phase chromatographic analysis Z-2- bromo -1- thiocyanate groups styrene yield is 62%.
Embodiment 10
Z-2- bromo -1- thiocyanate groups -4- methyl styrene,
(Z) preparation of -1- (2-bromo-l-thiocyanatovinyl) -4-methylbenzene:
In 10mL round-bottomed flask, 1- bromoacetylene base -4- toluene (195mg), potassium rhodanide (116mg), water are sequentially added
(18mg), azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), ultrasonic agitation (500 rev/min) of the gained mixed liquor in 30W/17KHz
It is reacted 15 minutes in reaction unit.Ethyl acetate extracts reactant, is dried in vacuo to obtain corresponding Z-2- bromo -1- thiocyanate groups
Styrene 238mg, yield 94%.
Embodiment 11
Z-2- bromo -1- thiocyanate groups -4- fluorobenzene ethene,
(Z) preparation of -1- (2-bromo-1-thiocyanatovinyl) -4-fluorobenzene
In 10mL round-bottomed flask, 1- bromoacetylene base -4- toluene fluoride (199mg) is sequentially added, potassium rhodanide (116mg),
Water (18mg), azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor 30W/17KHz ultrasonic agitation (500 turns/
Point) react 15 minutes in reaction unit.Ethyl acetate extracts reactant, is dried in vacuo to obtain corresponding Z-2- bromo -1- thiocyanic acid
Ester group styrene 239mg, yield 93%.
Embodiment 12
Z-3- (the bromo- 1- thiocyanate groups vinyl of 2-) thiophene
(Z) preparation of -3- (2-bromo-1-thiocyanatovinyl) thiophenee
In 10mL round-bottomed flask, 2- bromoacetylene base thiophene (187mg), potassium rhodanide (116mg), water are sequentially added
(18mg), azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), ultrasonic agitation (500 rev/min) of the gained mixed liquor in 30W/17KHz
It is reacted 18 minutes in reaction unit.Ethyl acetate extracts reactant, is dried in vacuo to obtain corresponding Z-2- bromo -1- thiocyanate groups
Styrene 228mg, yield 93%.
Embodiment 13
The bromo- 1- thiocyanate groups octene of Z-1-2-,
(Z) preparation of -1-bromo-2-thiocyanatohept-1-ene
In 10mL round-bottomed flask, 1- bromine octyne (189mg), potassium rhodanide (116mg), water (18mg), sulphur are sequentially added
Acid ion liquid (formula 3-A) (18.3mg), gained mixed liquor is in ultrasonic agitation (500 revs/min) reaction unit of 30W/17KHz
Reaction 20 minutes.Ethyl acetate extracts reactant, is dried in vacuo to obtain corresponding Z-2- bromo -1- thiocyanate groups styrene
225mg, yield 91%.
Embodiment 14
Z-2- chloro -1- thiocyanate groups styrene, (Z)-(2-chloro-1-thiocyanatovinyl) benzene
Preparation:
It in 10mL round-bottomed flask, sequentially adds phenyl chloroacetylene (136mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), ultrasonic agitation (500 revs/min) reaction unit of gained mixed liquor in 30W/17KHz
Middle reaction 15 minutes.Ethyl acetate extracts reactant, and vacuum drying Z-2- bromo -1- thiocyanate groups styrene 185mg is produced
Rate 95%.
Embodiment 15
Z-2- iodo -1- thiocyanate groups styrene, (Z)-(2-iodo-1-thiocyanatovinyl) benzene's
Preparation:
It in 10mL round-bottomed flask, sequentially adds phenyl iodoacetylene (228mg), potassium rhodanide (116mg), water (18mg),
Azochlorosulfonate acid ion liquid (formula 3-A) (18.3mg), ultrasonic agitation (500 revs/min) reaction unit of gained mixed liquor in 30W/17KHz
Middle reaction 15 minutes.Ethyl acetate extracts reactant, and vacuum drying Z-2- bromo -1- thiocyanate groups styrene 264mg is produced
Rate 92%.
In summary, under the catalysis of the ionic liquid, cooperate the ultrasonic wave and churned mechanically dual machine
Under system, it can be obviously improved the yield of product and the configuration preference of product, moreover, when can also be obviously shortened preparation
Between.In addition, azochlorosulfonate acid ion liquid catalyst can be recycled repeatedly, and catalytic performance is constant after by extraction product.The present invention
Preparation method, whole preparation process realizes solvent free, and reaction condition is mild, and substrate functional group excellent compatibility has
Higher application value.
Claims (10)
1. a kind of preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2-, it is characterised in that: will have 1 structure of formula
The halogenated alkynes of the 1- of formula, rhodanate, water and azochlorosulfonate acid ion liquid carry out addition reaction under ultrasound and stirring condition, and formula is made
Halogenated -1- thiocyanate groups the vinyl compound of the Z-2- of 2 structural formulas；
R is the alkyl or substituted hydrocarbon radical of C1~C30；X is Cl, Br or I.
2. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as described in claim 1, it is characterised in that:
R is alkyl, five yuan~seven yuan of naphthenic base, the cyclic hydrocarbon radical of unsaturated five yuan~seven yuan of part, benzene, five yuan~hexa-atomic
Heterocyclic aryl or by least two aromatic rings in phenyl ring, five-ring heterocycles, hexa-member heterocycle and close the condensed ring group of formation；
The alkyl, naphthenic base, cyclic hydrocarbon radical benzene, heterocyclic aryl, condensed ring group ring structure on allow containing substituent group；Institute
The substituent group stated is preferably H, C1~C6 alkyl, the alkoxy of C1~C6, hydroxyl, sulfydryl, methyl mercapto, trifluoromethylthio, cyanogen
Base, acyl group, C2~C30Ester group, trifluoromethyl, halogen or cyano.
3. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as claimed in claim 2, it is characterised in that:
The halogenated alkynes of the 1- has at least one of formula 1-A, the compound of structural formula of formula 1-B or formula 1-C；
R1~R7It is alone H, C1~C10Alkyl, C1~C10Alkyl oxygroup, C6~C20Aryl, C5~C20Heterocyclic aryl,
Hydroxyl, sulfydryl, methyl mercapto, trifluoromethylthio, cyano, acyl group, C2~C30Ester group, trifluoromethyl, halogen or cyano；
Or R1~R5In, adjacent group constitutes some or all of 5~10 yuan unsaturated cyclic structures together；Described
Also allow in cyclic structure containing hetero atom and substituent group；
Y is O, S, CH2Or NH.
4. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as claimed in any one of claims 1 to 3,
It is characterized in that: theoretical molar amount of the dosage of potassium rhodanide not less than reaction, it is preferable that the halogenated alkynes of potassium rhodanide, 1-
Molar ratio is not less than 1, preferably 1~2: 1；Further preferably 1.1~1.2: 1.
5. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as claimed in any one of claims 1 to 3,
Be characterized in that: the dosage of water not less than reaction theoretical molar amount, preferably 1~2: 1；Further preferably 1: 1.
6. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as described in claim 1, it is characterised in that:
The azochlorosulfonate acid ion liquid is at least one of the compound with structure described in formula 3；
R8For the alkyl of C1~C3；The integer that n is 1~4；
It is further preferred that the R8For methyl；N is 3.
7. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as described in claim 1 or 6, feature exist
In the molar ratio of: the halogenated alkynes of 1-, azochlorosulfonate acid ion liquid be 1: 0.1-0.3；Preferably 1: 0.1.
8. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as described in claim 1, it is characterised in that:
It is 20W, preferably 25~60W that the power of ultrasound, which is not less than,；
Supersonic frequency is not less than 15KHz；Preferably 17KHz~80KHz；
Preferably, the speed of agitator is preferably 300~750r/min.
9. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as claimed in claim 1 or 8, feature exist
In: the rhodanate is the alkali metal salt or ammonium salt of thiocyanate radical；Further preferably sodium sulfocyanate, potassium rhodanide,
At least one of ammonium thiocyanate.
10. the preparation method of the halogenated -1- thiocyanate groups vinyl compound of Z-2- as described in claim 1, it is characterised in that:
The addition reaction time is 15~35 minutes.
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| CN109912475A (en) * | 2019-03-25 | 2019-06-21 | 湖南科技学院 | A kind of environment-friendly preparation method thereof of Z-3- thiocyanate groups acrylamide compound |
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| CN109912474A (en) * | 2019-03-25 | 2019-06-21 | 湖南科技学院 | A kind of environment-friendly preparation method thereof of Z-3- thiocyanate groups acrylate compounds |
| CN109912475A (en) * | 2019-03-25 | 2019-06-21 | 湖南科技学院 | A kind of environment-friendly preparation method thereof of Z-3- thiocyanate groups acrylamide compound |
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