CN105418360B - A kind of method for preparing 1,1,1,3,3 pentachlorobutanes - Google Patents
A kind of method for preparing 1,1,1,3,3 pentachlorobutanes Download PDFInfo
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- CN105418360B CN105418360B CN201510765464.6A CN201510765464A CN105418360B CN 105418360 B CN105418360 B CN 105418360B CN 201510765464 A CN201510765464 A CN 201510765464A CN 105418360 B CN105418360 B CN 105418360B
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- carbon tetrachloride
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- 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
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
Abstract
The invention discloses a kind of method for preparing 1,1,1,3,3 pentachlorobutanes.This method is in the presence of telomerization catalyst, and carbon tetrachloride and 2 chloropropene telomerisation prepare 1,1,1,3,3 pentachlorobutane, and reaction temperature is 25~100 DEG C, and the reaction time is 0.5~5h；Telomerization catalyst is made up of major catalyst, co-catalyst and organic activator, wherein major catalyst is halo mantoquita or halo molysite, co-catalyst is alkylphosphonate, alkyl phosphite or trimethylamine, organic activator is azodiisobutyronitrile, 2, double (4 methoxyl groups 2 of 2 azos, 4 methyl pentane nitriles), the cyclohexanenitrile of 1,1 azo two, 2,3,4, the lactone of 5,6 penta hydroxy group, 2 hexenoic acid 4,2,3,4,5,6 pentahydroxy- ethylhexanals, phenylhydrazine or metoxyphenol, the mol ratio of major catalyst, co-catalyst and organic activator is 1:0.5~20:0.1~20.The telomerization catalyst that the present invention is used have the advantages that reaction condition it is gentle, to air-stable, available for catalysis carbon tetrachloride and 2 chloropropene telomerisation, 1,1,1,3,3 pentachlorobutane of preparation.
Description
Technical field
The present invention relates to the method that one kind prepares 1,1,1,3,3- pentachlorobutane, specifically refer in major catalyst, co-catalysis
In the presence of the telomerization catalyst of agent and organic activator composition, carbon tetrachloride prepares 1,1,1,3,3- five with the telomerization of 2- chloropropenes
The method of chlorobutane.
Background technology
1,1,1,3,3- pentachlorobutanes (HCC-360jfa) prepare 1,1,1,3,3- pentafluoropropanes (HFC-365mfc)
Intermediate.The HFC-365mfc latent value (ODP) of atmospheric ozone consumption is zero, and environmental-protecting performance is excellent, is 1,1,1- chloro fluoroethane
(HCFC-141b) and monofluorodichloromethane (CFC-11) ideal substitute, be widely used as foaming agent, solvent and cleaning agent.
It is main to use carbon tetrachloride with 2- chloropropenes for raw material in existing HCC-360jfa technologies of preparing, in catalyst
In the presence of telomerization synthesis obtain.Chinese patent CN1958541A reports carbon tetrachloride and synthesizes HCC- with 2- chloropropene telomerizations
360jfa method, using iron and frerrous chloride as catalyst, tributyl phosphite is co-catalyst, and reaction temperature is 100 DEG C, instead
9 hours between seasonable, the selectivity that the conversion ratio of 2- chloropropenes is 98.5%, HCC-360jfa is 95%.Above-mentioned document report
Prepare in HCC-360jfa technologies, iron powder used in catalyst system, in operating process iron powder exist easy occluding device and pipeline,
The problem of post processing is complicated, while iron powder easy oxidation by air, memory requirement in itself is high.
Chinese patent CN1629110A reports carbon tetrachloride and synthesizes 1,1,1,3,3- pentachlorobutanes with 2- chloropropene telomerizations
Method, the reaction carries out in the presence of acetonitrile, stannous chloride and tert-butylamine, 130~140 DEG C of 8 hours of reaction, HCC-
360jfa yields are 96.2%.The HCC-360jfa technologies that prepare of above-mentioned document report have the shortcomings that reaction temperature is higher, together
When the easy oxidation by air of telomerization catalyst stannous chloride, be difficult storage.
The content of the invention
It is an object of the invention to overcome deficiency present in background technology there is provided a kind of reaction condition it is gentle, to air
Stable telomerization catalyst, and use the catalyst carbon tetrachloride and 2- chloropropenes telomerization 1,1,1,3,3- pentachloro- of preparation
The method of butane.
In order to realize the purpose of the present invention, the method for the pentachloropropane (HCC-240fa) of preparation 1,1,1,3,3- of the invention,
The telomerization catalyst being made up of major catalyst, co-catalyst and organic activator is constructed, and is urged using the telomerization catalyst
Change carbon tetrachloride and prepare HCC-360jfa with the telomerization of 2- chloropropenes.
Described major catalyst is the halo mantoquita or halo molysite of high-valence state, and specific preferred halo mantoquita is chlorination
Copper, copper bromide, halo molysite preferably is iron chloride or ferric bromide, and preferred halo mantoquita is copper chloride, preferred halogen
It is iron chloride for molysite.
Described co-catalyst dissolves in major catalyst the organic ligand of reaction system to be coordinated with major catalyst,
Suitable co-catalyst is alkylphosphonate, alkyl phosphite or trimethylamine.Specific preferred alkylphosphonate is phosphoric acid
Triethyl, tributyl phosphate or triphenyl phosphate, specific preferred alkyl phosphite are triethyl phosphite or phosphorous acid three
Butyl ester；Specific preferred trimethylamine is 2,2'- bipyridyls, three (2- (methylamino) ethamine, N, N, N', N', N "-pentamethyl
Diethylenetriamines, 1,1,4,7,10,10- hexamethyl triethylene tetramines or three (2- pyridylmethyls) amine.
Described organic activator, which is, to be the lower valency metal salt with telomerization catalytic activity by major catalyst activation
Organic matter, and be dissolvable in water reaction system, specific selected organic activator is azodiisobutyronitrile, the double (4- of 2,2- azos
Methoxyl group -2,4- methyl pentane nitriles), the cyclohexanenitrile of 1,1- azos two, 2,3,4,5,6- penta hydroxy group -2- hexenoic acid -4- lactones, 2,3,
4,5,6- pentahydroxy-s ethylhexanal, phenylhydrazine or metoxyphenol.
The mol ratio of major catalyst, co-catalyst and organic activator is 1 in the telomerization catalyst:0.5~20:0.1
~20, mol ratio preferably is 1:1~5:0.5~10.The major catalyst of addition and the mol ratio of carbon tetrachloride be 0.001~
0.5:1, mol ratio preferably is 0.005~0.1:1.
The present invention carries out telomerisation using the excessive method of carbon tetrachloride, and the mol ratio of 2- chloropropenes and carbon tetrachloride is
0.1~1:1, mol ratio preferably is 0.3~0.8:1.
The reaction temperature of telomerisation is 25~100 DEG C, and the reaction time is 0.5~5h.It is preferred that reaction temperature for 50~
80 DEG C, the reaction time preferably is 1~3h.
The telomerisation of carbon tetrachloride and 2- chloropropenes can in organic solvent or it is solvent-free it is middle carry out, when using organic
During solvent, optional organic solvent is acetonitrile, ethylene glycol, ethanol, acetone, petroleum ether, toluene, DMF or two
First sulfoxide.The usage amount of solvent is the 10%~200% of carbon tetrachloride mass fraction.
The telomerisation of carbon tetrachloride and 2- chloropropenes be able to can also be operated continuously with intermittently operated, and reaction is in itself to reaction
Form is without obvious requirement.
A kind of preferred method for preparing 1,1,1,3,3- pentachlorobutanes：With iron chloride, the cyclohexanenitrile of 1,1- azos two and phosphorus
In the presence of the telomerization catalyst of sour tributyl composition, carbon tetrachloride prepares 1,1,1,3,3- five neoprene with the telomerisation of 2- chloropropenes
The mol ratio of alkane, wherein iron chloride, the hexamethylene of 1,1- azos two and tributyl phosphate is 1:1:3, iron chloride and carbon tetrachloride rub
You are than being 0.01:The mol ratio of 1,2- chloropropene and carbon tetrachloride is 0.5:1, reaction temperature is 80 DEG C, and the reaction time is 1h.
A kind of preferred method for preparing 1,1,1,3,3- pentachlorobutanes：In copper chloride, azodiisobutyronitrile and three (2-
In the presence of the telomerization catalyst of (methylamino) ethamine composition, carbon tetrachloride prepares 1,1,1,3,3- with the telomerisation of 2- chloropropenes
(mol ratio of 2- (methylamino) ethamine is 1 by pentachlorobutane, wherein copper chloride, azodiisobutyronitrile and three：1：1, iron chloride with
The mol ratio of carbon tetrachloride is 0.01:The mol ratio of 1,2- chloropropene and carbon tetrachloride is 0.5:1, reaction temperature is 60 DEG C, instead
It is 1h between seasonable.
Advantages of the present invention：(1) urged using the new telomerization being made up of major catalyst, co-catalyst and organic activator
Agent, the catalyst dissolution forms homogeneous catalysis system in reaction system, in the absence of the occluding device and pipe existed using iron powder
The problem of road, complicated post processing；(2) new telomerization catalyst has very high catalytic activity, and reaction temperature is 25~100 DEG C,
Reaction time is 0.5~5h, and reaction temperature is 50~80 DEG C under the preferred conditions, and the reaction time is 1~3h, in some conditions
Lower reaction can even be carried out at room temperature, namely compared to documents reaction condition milder；(3) in new telomerization catalyst
Major catalyst be high-valence state metal salt, iron powder, the stannous chloride of the lower valency used compared to documents are difficult by air
Oxidation, is more easy to storage.
Embodiment
It is following that the present invention is described in further detail in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
By major catalyst iron chloride 8.13g (0.05mol), co-catalyst tributyl phosphate 39.9g (0.15mol), organic
The cyclohexanenitrile 12.2 (0.05mol) of activator 1,1- azos two and carbon tetrachloride 770g (5mol) are sequentially added to 1L stainless steel high pressures
Reactor.Enclosed high pressure kettle, opens stirring, with the air in nitrogen displacement autoclave, replaces three times.It is then disposable to add 2-
Chloropropene 156.25g, is heated to 80 DEG C, reaction terminates after 1 hour by temperature of reactor.Treat that autoclave is down to room temperature, unload kettle and take
Go out material.Fluid sample is taken with pipette, is analyzed by chromatographic process, the conversion ratio of 2- chloropropenes is 96%, HCC-360jfa
Selectivity be 97%.
Embodiment 2
The operating process of embodiment 2 is similar to Example 1, except that major catalyst is ferric bromide.Product passes through color
Spectral Analysis, the selectivity that the conversion ratio of 2- chloropropenes is 94.5%, HCC-360jfa is 94.3%.
Embodiment 3~9
The operating process of embodiment 3~9 is similar to Example 1, except that change co-catalyst and organic activator,
And adjust reaction temperature to match the activity of telomerization catalyst.Reaction result is as shown in table 1.
Table 1
Embodiment 10
By major catalyst copper chloride 6.73g (0.05mol), (2- (methylamino) the ethamine 11.52g of co-catalyst three
(0.05mol), organic activator azodiisobutyronitrile 12.2 (0.05mol) and carbon tetrachloride 770g (5mol) add stainless to 1L
Steel autoclave.Enclosed high pressure kettle, opens stirring, with the air in nitrogen displacement autoclave, replaces three times.It is then disposable
2- chloropropene 156.25g are added, temperature of reactor 60 DEG C are heated to, reaction terminates after 1 hour.Treat that autoclave is down to room temperature,
Unload kettle and take out material.Fluid sample is taken with pipette, and is analyzed by chromatographic process, the conversion ratio of 2- chloropropenes is 97.6%,
HCC-360jfa selectivity is 98.2%.
Embodiment 11
The operating process of embodiment 11 is similar to Example 10, except that major catalyst is copper bromide.Product passes through
Chromatographic process is analyzed, and the selectivity that the conversion ratio of 2- chloropropenes is 95.6%, HCC-360jfa is 95.9%.
Embodiment 12~21
The operating process of embodiment 12~21 is similar to Example 10, except that changing co-catalyst and organic active
Agent, and adjust reaction temperature to match the activity of telomerization catalyst.Reaction result is as shown in table 2.
Table 2
Embodiment 22~27
The operating process of embodiment 22~27 is similar to Example 10, except that changing reaction condition.Reaction result
As shown in table 3.
Table 3
Embodiment 28
The operating process of embodiment 28 is similar to Example 10, except that adding 200g acetonitriles is used as solvent.Product
Analyzed by chromatographic process, the selectivity that the conversion ratio of 2- chloropropenes is 94.6%, HCC-360jfa is 94.9%.
Embodiment 29
The operating process of embodiment 29 is similar to Example 10, except that adding 250g DMFs
It is used as solvent.Product is analyzed by chromatographic process, and the conversion ratio of 2- chloropropenes is for 96.6%, HCC-360jfa selectivity
95.2%.
Embodiment 30
The operating process of embodiment 30 is similar to Example 10, except that adding 250g toluene is used as solvent.Product
Analyzed by chromatographic process, the selectivity that the conversion ratio of 2- chloropropenes is 83.6%, HCC-360jfa is 96.2%.
Claims (4)
1. the method that one kind prepares 1,1,1,3,3- pentachlorobutane, it is characterised in that in the presence of telomerization catalyst, carbon tetrachloride
With the telomerisation of 2- chloropropenes prepare 1,1,1,3,3- pentachlorobutane, reaction temperature be 25~100 DEG C, the reaction time be 0.5~
5h；Telomerization catalyst is made up of major catalyst, co-catalyst and organic activator, and wherein major catalyst is halo mantoquita or halo
Molysite, halo mantoquita is copper chloride or copper bromide, and halo molysite is iron chloride or ferric bromide；Co-catalyst be alkylphosphonate,
Alkyl phosphite or trimethylamine, organic activator are azodiisobutyronitrile, double (4- methoxyl group -2, the 4- diformazans of 2,2- azos
Base valeronitrile), the cyclohexanenitrile of 1,1- azos two, 2,3,4,5,6- penta hydroxy group -2- hexenoic acid -4- lactones, 2,3,4,5,6- penta hydroxy group second
Aldehyde, phenylhydrazine or metoxyphenol, the mol ratio of major catalyst, co-catalyst and organic activator is 1:0.5~20:0.1~20,
The mol ratio of major catalyst and carbon tetrachloride is 0.001~0.5:The mol ratio of 1,2- chloropropene and carbon tetrachloride is 0.1~1:
1。
2. the method according to claim 1 for preparing 1,1,1,3,3- pentachlorobutane, it is characterised in that described co-catalysis
Alkylphosphonate is triethyl phosphate, tributyl phosphate or triphenyl phosphate in agent；Alkyl phosphite is triethyl phosphite
Or tributyl phosphite；Trimethylamine is 2,2'- bipyridyls, three (2- (methylamino) ethamine, N, N, N', N', N "-pentamethyl
Diethylenetriamines, 1,1,4,7,10,10- hexamethyl triethylene tetramines or three (2- pyridylmethyls) amine.
3. it is according to claim 1 or 2 prepare 1,1,1,3,3- pentachlorobutane method, it is characterised in that with iron chloride,
In the presence of the telomerization catalyst of tributyl phosphate and the cyclohexanenitrile of 1,1- azo two composition, carbon tetrachloride and 2- chloropropene telomerisation
1,1,1,3,3- pentachlorobutane is prepared, the wherein mol ratio of iron chloride, tributyl phosphate and the cyclohexanenitrile of 1,1- azo two is 1:3:
1, the mol ratio of iron chloride and carbon tetrachloride is 0.01:The mol ratio of 1,2- chloropropene and carbon tetrachloride is 0.5:1, reaction temperature
For 80 DEG C, the reaction time is 1h.
4. it is according to claim 1 or 2 prepare 1,1,1,3,3- pentachlorobutane method, it is characterised in that with copper chloride,
Three (in the presence of the telomerization catalyst of 2- (methylamino) ethamine and azodiisobutyronitrile composition, carbon tetrachloride and 2- chloropropenes tune
Poly- reaction prepares 1,1,1,3,3- pentachlorobutane, wherein copper chloride, three (2- (methylamino) ethamine and azodiisobutyronitrile rub
You are than being 1:1:1, the mol ratio of copper chloride and carbon tetrachloride is 0.01:The mol ratio of 1,2- chloropropene and carbon tetrachloride is 0.5:
1, reaction temperature is 60 DEG C, and the reaction time is 1h.
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