CN108707059A - A method of cis- 1,1,1,4,4,4- hexafluoros -2- butylene is prepared by maleic acid - Google Patents
A method of cis- 1,1,1,4,4,4- hexafluoros -2- butylene is prepared by maleic acid Download PDFInfo
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- CN108707059A CN108707059A CN201810676103.8A CN201810676103A CN108707059A CN 108707059 A CN108707059 A CN 108707059A CN 201810676103 A CN201810676103 A CN 201810676103A CN 108707059 A CN108707059 A CN 108707059A
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- maleic acid
- butylene
- nitrae
- hexafluoro
- isosorbide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses one kind preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, and 4, the method of 4- hexafluoro -2- butylene obtains cis- 1,1 under cuprous salt catalysis using maleic acid as starting material with hypervalent iodine reagent generation decarboxylation-trifluoromethylation reaction process, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.It is an advantage of the invention that：The present invention is raw material using maleic acid cheap and easy to get, and does not use the higher fluorination reagent of toxic side effect, and byproduct of reaction is substantially non-toxic, to improve production security；Meanwhile hypervalent iodine reagent used（Togni reagent I and Togni reagents II）Property is stable, reactivity worth is good；In addition, product keeps cis-configuration identical with raw material, reaction selectivity high.
Description
Technical field
The present invention relates to a kind of fine chemical products（Foaming agent, refrigerant）Preparation method, and in particular to one kind by Malaysia
The method that acid prepares cis- 1,1,1,4,4,4- hexafluoros -2- butylene.
Background technology
Cis- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene (Z-HFO-1336) belong to HF hydrocarbon (HFO) substance, are new one
For environmentally protective foaming agent, structure such as following formula（Ⅰ）It is shown：
Compared with the first, second and third generation foaming agent, Z-HFO-1336 has the characteristics that four aspects：（1）It is less toxic, non-combustible；（2）Ozone
The latent value (ODP) of consumption is zero；（3）The latent value (GWP ≈ 9) of greenhouse effects is extremely low；（4）Boiling point (33 DEG C) is close with room temperature.It is sent out
Bubble, heat-proof quality are excellent, and effect on environment very little, so being counted as new generation of green environment-friendly foaming agent, preparation method
By the extensive concern of fluorine chemical circles.
Currently, Journal of Fluorine Chemistry (2016), 191,77-83 and《Chemical industry is in progress》,
(2014), 33 (1), 193-197 and《Organic fluoride industry》, 2016 (1), the system of the Z-HFO-1336 of the reports such as 32-37
Preparation Method is broadly divided into three kinds：（1）It is prepared by directly fluorination C4 compounds；（2）Freon class compound CFC-113, HCFC-123
It is prepared through coupling reaction；（3）It is prepared through telomerisation with alkenyl halide by halide.These methods respectively have excellent, disadvantage.
In the above method, only have an example by the preparation method of raw material of maleic acid, in J. Am. Chem. Soc.,
(1960), 82,543-551 and Wang, C L J. Fluorination by sulfur tetrafluoride[J].
It is reported in Organic Reactions (1985) (Hoboken, NJ, United States), the method is with SF4For fluorine
Change reagent, cis- 1,1 is prepared by one step of direct fluorination, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.It is shown below：
The method product can keep cis-configuration identical with raw material, but there are SF4The toxicity of gas is big and dosage is more, generation
A large amount of SOF2With the shortcomings of HF is big to the harm of environment, generation safety is relatively low.
Invention content
In order to solve the above technical problems, the present invention provides one kind cis- 1,1 is prepared by maleic acid, Isosorbide-5-Nitrae, 4,4- hexafluoro -2-
The method of butylene, reagent has no toxic side effect, good reaction selectivity, generate it is safe.
The technical solution adopted by the present invention is：
One kind preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, using maleic acid as starting material, in Asia
Mantoquita catalysis is lower and hypervalent iodine reagent occurs decarboxylation-trifluoromethylation reaction process and obtains cis- 1,1,1,4,4,4- hexafluoros -2- fourths
Alkene.
Further, hypervalent iodine reagent is selected from 1- (trifluoromethyl) -3,3- dimethyl -1,2- benzo iodine oxa-, penta ring
One or both of -3 (1H) -one (Togni reagent II) of (Togni reagent I) and 1- (trifluoromethyl) -1,2- benzenesulfonyls.
Further, cuprous salt catalyst selected from stannous chloride, cuprous bromide, cuprous iodide and nitrilation it is cuprous in one kind
Or it is several.
Further, the molar ratio of maleic acid and hypervalent iodine reagent is 1:2 ~ 1:6.
Further, the molar ratio of maleic acid and cuprous salt catalyst is 1:0.1 ~ 1:0.3.
Further, reaction temperature is 100 ~ 120 DEG C.
Further, one kind in n,N-Dimethylformamide and dimethyl sulfoxide of the reaction dissolvent in preparation process or
Two kinds.
The beneficial effects of the invention are as follows：The present invention is raw material using maleic acid cheap and easy to get, and does not use toxic side effect
Higher fluorination reagent, byproduct of reaction is substantially non-toxic, to improve production security；Meanwhile hypervalent iodine reagent used
（Togni reagent I and Togni reagents II）Property is stable, reactivity worth is good；In addition, product keeps cis- structure identical with raw material
Type, reaction selectivity are high.
Specific implementation mode
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment
It is only used for explaining the present invention, not restrict the protection scope of the present invention.
One kind preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, using maleic acid as starting material,
Decarboxylation-trifluoromethylation reaction process occurs with hypervalent iodine reagent under cuprous salt catalysis and obtains cis- 1,1,1,4,4,4- hexafluoros-
2- butylene, concrete operation step are as follows：
Embodiment 1
In autoclave, 150 mL dimethyl sulfoxides are first added under nitrogen protection, then be separately added into stannous chloride（0.369
g, 4.0 mmol）With penta ring of 1- (trifluoromethyl) -3,3- dimethyl -1,2- benzo iodine oxa-（26.40 g, 80.0 mmol）.
Maleic acid is slowly added dropwise under stirring into said mixture again（4.64 g, 40.0 mmol）Dimethyl sulfoxide（50 mL）Solution.
After being added dropwise, mixed liquor is heated to 100 DEG C of 24 h of reaction under stirring.It is down to normal temperature and pressure after reaction, distillation is collected
32-35 DEG C of fraction obtains cis- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro-2- butylene, yield：48.7%.
Embodiment 2
In autoclave, first it is added 120 mL's under nitrogen protectionN,NDimethylformamide is separately added into iodate Asia
Copper（2.28 g, 12.0 mmol）With 1- (trifluoromethyl) -1,2- benzenesulfonyls -3 (1H) -one（50.56 g, 160.0 mmol）.
Maleic acid is slowly added dropwise under stirring into said mixture again（4.64 g, 40.0 mmol）'sN,NDimethylformamide（50
mL）Solution.After being added dropwise, mixed liquor is heated to 120 DEG C of 48 h of reaction under stirring.It is down to normal temperature and pressure after reaction,
Distillation collects 32-35 DEG C of fraction and obtains cis- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro-2- butylene, yield：67.2 %.
Embodiment 3
In autoclave, first it is added 200 mL's under nitrogen protectionN,NDimethylformamide is separately added into protobromide
Copper（1.72 g, 12.0 mmol）With penta ring of 1- (trifluoromethyl) -3,3- dimethyl -1,2- benzo iodine oxa-（79.22 g,
240.0 mmol）.Maleic acid is slowly added dropwise under stirring into said mixture again（4.64 g, 40.0 mmol）'sN,NDiformazan
Base formamide（50 mL）Solution.After being added dropwise, mixed liquor is heated to 120 DEG C of 48 h of reaction under stirring.After reaction
It is down to normal temperature and pressure, distillation collects 32-35 DEG C of fraction and obtains cis- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro-2- butylene, yield：68.5
%。
Claims (7)
1. a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, which is characterized in that be with maleic acid
Starting material, under cuprous salt catalysis decarboxylation-trifluoromethylation reaction process occurs with hypervalent iodine reagent obtains cis- 1,1, Isosorbide-5-Nitrae,
4,4- hexafluoro -2- butylene.
2. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, hypervalent iodine reagent is selected from 1- (trifluoromethyl) -3,3- dimethyl -1,2- benzo iodine oxa-, penta ring (Togni reagent I)
One or both of with -3 (1H) -one (Togni reagent II) of 1- (trifluoromethyl) -1,2- benzenesulfonyls.
3. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, it is one or more of cuprous that cuprous salt catalyst is selected from stannous chloride, cuprous bromide, cuprous iodide and nitrilation.
4. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, the molar ratio of maleic acid and hypervalent iodine reagent is 1:2 ~ 1:6.
5. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, the molar ratio of maleic acid and cuprous salt catalyst is 1:0.1 ~ 1:0.3.
6. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, reaction temperature is 100 ~ 120 DEG C.
7. it is according to claim 1 it is a kind of preparing cis- 1,1 by maleic acid, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene,
It is characterized in that, the reaction dissolvent in preparation process is selected fromN,NOne or both of dimethylformamide and dimethyl sulfoxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810676103.8A CN108707059A (en) | 2018-06-27 | 2018-06-27 | A method of cis- 1,1,1,4,4,4- hexafluoros -2- butylene is prepared by maleic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810676103.8A CN108707059A (en) | 2018-06-27 | 2018-06-27 | A method of cis- 1,1,1,4,4,4- hexafluoros -2- butylene is prepared by maleic acid |
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| CN108707059A true CN108707059A (en) | 2018-10-26 |
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