Title of Invention

A PROCESS FOR THE PREPARATION OF 1,1,1,3,3-PENTACHLOROBUTANE

Abstract The invention ~'elates to the preparation of l,l,l,3,3-pentachlorobutane and 1,1,1,3,3- pentafluorobutane. 1, 1, 1, 3, 3-pentachlorobutane, whose fluorination leads to l,l,l,3,3-pentafluorobutane, is prepared by addition of carbon tetrachloride to 2- chloropropene in the presence of a copper salt and an amine. The l,l,l,3,3-pentachlorobutane is prepared with high yield and selectivity.
Full Text

The present invention relates to the preparation of 1,1,1,3,3-pentachlorobutane and to its fluorination to 1,1/1,3,3-pentafluorobutane•
With a boiling point of 40°C, 1,1,1,3,3-pentafluorobutane (known under the name F365 mfc) is a potential substitute for liquid chlorofluoroalkanes which are banned by the Montreal Protocol, most particularly fluorotrichloromethane (Fll; b.p. = 27°C) and trichlorotrifluoroethane (F113; b.p. = 47°C).
Processes allowing F365 mfc to be prepared are few in number and generally involve the fluorination of a chloro precursor such as 2,2-difluoro-4,4,4-trichlorobutane, 2-bromo-2,4,4,4-tetrachlorobutane or 1,1,1,3,3-pentachlorobutane.
Henne et al. (J. Am. Chem. Soc. 67, p. 1194-1197 and 1197-1199, 1945) chlorinate 2,2-difluorobutane to obtain, with a selectivity of 52.5%, 2,2-difluoro-4,4,4-trichlorobutane (F362 jfc) which is then fluorinated to F365 mfc. McBee and Hausch (Ind. Eng. Chem. 39, p. 418-420, 1947) fluorinate F362 jfc with HF/HgO or with the mixture SbF3/SbCl5, but the fluorination yields do not exceed 15%. All these processes* are characterized by low yields, essentially due to the lack of selectivity of the chlorination reactions leading to the chloro precursor.
Another method for the preparation of F365 mfc, described by Tarrant et al. (J. Am. Chem. Soc. 80, p.1711-1713, 1958), consists of the radical

addition of CCl3Br to 2-chloropropene and fluorination with HF, in the absence of catalyst, "of the 1:1 addition product (CCl3CH2CBrClCH3) obtained, in a yield of 34%. This method does not improve the overall yield since, in this case, a lack of selectivity is observed due to the formation of telomere promoted by the radical initiation with benzoyl peroxide*
Another chloro precursor of F365 mfc is 1,1,1,3,3-pentachlorobutane which, according to Friedlina et al. [Izv Akad. Nauk SSSR (6), p. 1333-1336 (1980) and (8), p. 1903-5 (1979)], may be obtained by telomerization of vinylidene chloride with 1,1,1-trichloroethane or that of 2-chloropropene with CC14 in the presence of iron pentacarbonyl. In both cases, a mixture of three telomers is obtained and the selectivity towards 1,1,1,3,3-pentachlorobutane (1:1 addition product) is insufficient to be of any definite economic value.
The direct preparation of F365 mfc according to the method of Bloshchitsa et al. (Zhur. Org. Khim 24(7), p. 1558, 1988) by the action of hydrofluoric acid and sulphur tetrafluoride on diketene constitutes, in point of fact, the only method leading to F365 mfc with an acceptable yield (70%). Unfortunately, this process uses two relatively uncommon starting materials, diketene and sulphur tetrafluoride.
F365 mfc is also a by-product in the manufacture of 1,1-dichloro-l-fluoroethane (F141b), but

the similarity of their boiling points (F141b : b.p. = 32°C; F365 mfc : b.p. = 40°C) and the existence of a minimum-boiling-point azeotropic mixture do not allow ready separation of the two products. A separation process, based on the principle of distillation in the presence of an excess of HF, is however described in European patent EP 395,793.
Amine/cuprous salt complexes are known catalysts for the addition of polyhalo compounds to olefins (Kotora et al., J. of Molecular Catalysis 77, p. 51-61, 1992), but these authors show that the yield of 1:1 addition product may pass from 97% for vinyl chloride to 11% for 1,2-dichloroethylene.
While investigating a process allowing F365 mfc to be prepared in high yield and selectivity, it has now been found that 2-chloropropene is classed among the olefins which are reactive towards carbon tetrachloride and may, under certain conditions, lead to the expected 1:1 addition product, 1,1,1,3,3-pentachlorobutane, in excellent yield and with an excellent selectivity, the formation of by-products, telomers or elimination products being negligible. Furthermore, among these by-products, the C4H4C14 olefins which may be formed by dehydrochlorination of 1,1,1,3,3-pentachlorobutane are readily fluorinated to 1,1,1,3,3-pentafluorobutane.
According to one aspect of the present
*
invention, there is provided a process for the

preparation of 1,1,1,3,3-pentachlorobutane which process comprises adding carbon tetrachloride to 2-chloropropene, in the presence of a copper salt and an amine.
According to another aspect of the present invention there is provided a process for the preparation of F365 mfc, comprising addition of carbon tetrachloride to 2-chloropropene and fluorination with hydrofluoric acid of the 1,1,1,3,3-pentachlorobutane thus obtained.
A cuprous salt, preferably a halide and more particularly cuprous chloride, is advantageously used as copper salt.
The amine to be used may be a mono-, di- or trialkylamine whose linear or branched alkyl radical(s) may contain from 1 to 8 (preferably 2 to 4) carbon atoms. A cyclanic amine, for example cyclohexylamine, may also be used. A primary amine, and more particularly isopropylamine, is advantageously used.
The 2-chloropropene may be obtained in a manner which is known per se, by dehydrochlorination of 1,2-dichloropropane or of 2,2-dichloropropane (thermally or by the action of glycolic potassium hydroxide) or, preferably, by the action of phenylchloroform on acetone in the presence of a Lewis acid such as zinc chloride or ferric chloride (French Patent Specification FR 2,213,257); in this case, the yield of 2-chloro-propene reaches 77% and the main by-

1
product of the reaction, 2,2-dichloropropane, may readily be converted into 2-chloropropene by elimination of HC1 according to the process with glycolic sodium hydroxide or potassium hydroxide described in US patent 2,543,648*
The CC14/CH3CC1 = CH2 molar ratio may range from 2 to 6 but is preferably between 2.5 and 4.5.
The copper salt, in particular the cuprous chloride, has the role of initiating the formation of the trichloromethyl radical and of ensuring transfer of the chlorine to the CC13CH2CC1CH3 radical resulting from the addition of the CC13 radical to 2-chloropropene. It is generally used in an amount such that the molar ratio: copper salt/2-chloropropene is suitably between 0.001 and 0.05, preferably between 0.005 and 0.02.
The amine concentration has a dominant influence on the yield of 1,1,1,3,3-pentachlorobutane. Relative to the total number of moles of the initial reaction mixture (CC14 + CH3CC1 ■ CH2 + CuCl + amine), it may suitably range from 0.5 to 10%, but is preferably between 1 and 8% and, more particularly, between 2.5 and 6%.
The reaction may be carried out at a temperature of between 80 and 130°C, but is preferably carried out at between 90 and 110°C.
The 1,1,1,3,3-pentachlorobutane formed, which may be separated from the reaction mixture by processes that are known per se, in particular by filtration,

acidic washing, washing with water, drying and distillation, is used in accordance with a second aspect of the present invention for the synthesis of 1,1,1,3,3-pentafluorobutane by fluorination using hydrofluoric acid.
This operation may be performed in the liquid phase, in the presence or absence of catalysts. It is generally carried out under autogenous pressure at a temperature of between 80 and 120°C, preferably at about 100°C. The HF/CCl3CH2CClaCH3 molar ratio may range from 15 to 30, but is advantageously between 20 and 25. Any liquid-phase fluorination catalyst may be used as catalyst, in particular an antimony-based catalyst. However, the best results have been obtained without catalyst.
The examples which follow illustrate the invention without limiting it. EXAMPLE 1
8 mg of cuprous chloride, 117 mg of n-butylamine, 370 mg of 2-chloropropene (destabilized beforehand by distillation) and, lastly, 3.2 g of carbon tetrachloride were successively introduced into a thick-walled Pyrex tube maintained at 0°C. The tube was then sealed, homogenized and heated at constant temperature (100°C) for 4 hours with stirring.
After cooling, the tube was opened on a gas manifold, allowing the gas phase to be recovered quantitatively, the liquid phase being transferred into

a flask for separate analysis. The two phases were analysed by gas chromatography and the reaction balance was reconstituted from these analyses.
The results of this test (Test 1-a), as well as the operating conditions and the results obtained with other amines (Tests 1-b to 1-g), are summarized in Table (I), in which the abbreviations have the following meanings:
DC , : degree of conversion
360 jfas 1,1,1,3,3-pentachlorobutane





(0.077 mol) of isopropylamine were successively introduced into a 500 ml three-necked round-bottomed flask equipped with a condenser at -25°C and a dropping funnel, followed, after stirring, by 180,5 g of CC14 (1.17 mol). 29.6 g (0.38 mol) of 2-chloropropene were then introduced into the bright-blue solution and the reaction medium was heated at 100°C for two hours and thirty minutes.
After stopping the heating and cooling for 6 hours, the reaction mixture was filtered through "Decalite" until the blue-green colour disappeared, then washed twice with IN hydrochloric acid to remove the traces of unreacted amine. The organic phase was then washed with water until neutral and dried over sodium sulphate. The 1,1,1,3,3-pentachlorobutane was then separated from the excess CC14 by distillation under vacuum between room temperature and 50°C.
Along with 1.4 g of unreacted 2-chloropropene (DC = 95.3%), 79 g of 1,1,1,3,3-pentachlorobutane, 1.7 g of C4C14H4 olefin and 2.7 g of heavy telomers including 90% of dimer were obtained. The purity of the 360 jfa thus obtained by distillation reaches 98% and the degree of conversion of the 2-chloropropene into 360 jfa is 88.6%; if it is considered that the olefin becomes fluorinated into F365 mfc in the same manner as 360 jfa, the overall yield reaches 90.8% under these conditions.

EXAMPLE 4
41.1 g of 1,1,1,3,3-pentachlorobutane (0.178 mol) and 82.2 g of anhydrous hydrofluoric acid (4.108 mol) were successively introduced into an 800 ml 316 litre stainless steel autoclave equipped with a pressure indicator, a thermometer probe, a cracking disc and a system for stirring with a magnetic stirrer-bar.
With the reactor heated to 100°C, the pressure gradually rose to reach 30.4 bar. After 8 hours the reaction system was cooled to room temperature and a residual pressure of 12.8 bar was observed.
The light organic compounds (23.2 g) and the hydracids (96.8 g) were removed by degassing and then flushing with helium. The heavy products (2 g) were collected after opening the autoclave.
Analysis of the various phases collected allowed a degree of conversion of the 1,1,1,3,3-pentachlorobutane and a selectivity towards 1,1,1,3,3-pentafluorobutane to be calculated, these respectively reaching 98.1% and 61%.
The other reaction products were mainly tinder-fluorinated compounds: C4H5C1F4 (selectivity = 14.8%), C4H5C12F3 (2 isomers: selectivity = 17.8%) and C4H5C13F2 (selectivity = 1%) . These compounds may advantageously be recycled into the reactor in order to be converted into 1,1,1,3,3-pentafluorobutane.




WE CLAIM;
1. Process for the preparation of
1,1/1,3,3-pentachlorobutane which process comprises adding carbon tetrachloride to 2-chloropropene in the presence of a copper salt and an amine.
2. Process according to Claim 1, in which the copper salt is cuprous chloride.
3. Process according to Claim 1 or 2, in which the amine is a primary amine containing from 1 to 8 carbon atoms.
4. Process according to Claim 1 or 2, in which the amine is a primary alkylamine containing 2 to 4 carbon atoms.
5. Process according to Claim 1 or 2, in which the amine is isopropylamine.
6. Process according to any one of the preceding Claims, in which the CC14/CH3CC1=CH2 molar ratio is between 2 and 6.
7. Process according to any one of Claims 1 to 5, in which the CC14/CH3CC13=BCH2 molar ratio is between 2.5 and 4.5.
8. Process according to any one of the preceding Claims, in which the molar ratio: copper salt/2-chloropropene is between 0.001 and 0.05.
9. Process according to any one of Claims 1 to 7, in which the molar ratio: copper salt/2-chloropropene is between 0.005 and 0.02.

10. Process according to any one of the preceding Claims, in which the molar concentration of amine is between 0.5 and 10%.
11. Process according to any one of Claims 1 to 9, in which the molar concentration of amine is between 1 and 8%.
12. Process according to any one of Claims 1 to 9, in which the molar concentration of amine is between 2.5 and 6%.
13. Process according to any one of the preceding Claims, which process is performed at a temperature of between 80 and 130°C.
14. Process according to any one of Claims 1 to 12, which process is performed at a temperature between 90 and 110°C.
15. Process for the preparation of 1,1,1,3,3-pentafluorobutane, which process comprises subjecting to fluorination with hydrofluoric acid 1,1,1,3,3-pentachlorobutane obtained by a process according to any one of Claims 1 to 14.
16. Process according to Claim 15, in which the fluorination is carried out in the liquid phase at a temperature ranging approximately from 80 to 120°C.
17. Process according to Claim 15 in which the fluorination is carried out in the liquid phase at a temperature of approximately 100°C.
18. Process according to any one of Claims 15 to 17, in which the HF/CC13CH2CC12CH3 molar ratio is

from 15 to 30.
19, Process according to any one of Claims 15 to 17, in which the HF/CC13CH2CC12CH3 molar ratio is between 20 and 25.
[email protected]# pcooess im the.preparation of 1i1#1*3#3#~ pentachlorobutane substantially as herein described and exemplified*


Documents:

198-mas-1997- abstract.pdf

198-mas-1997- claims dulpicate.pdf

198-mas-1997- claims original.pdf

198-mas-1997- correspondence others.pdf

198-mas-1997- correspondence po.pdf

198-mas-1997- description complete duplicate.pdf

198-mas-1997- description complete original.pdf

198-mas-1997- form 1.pdf

198-mas-1997- form 26.pdf

198-mas-1997- form 3.pdf

198-mas-1997- form 4.pdf


Patent Number 206480
Indian Patent Application Number 198/MAS/1997
PG Journal Number 26/2007
Publication Date 29-Jun-2007
Grant Date 27-Apr-2007
Date of Filing 31-Jan-1997
Name of Patentee M/S. ELF ATOCHEM S. A .
Applicant Address 4 & 8 COURS MICHELET LA DEFENSE 10 92800
Inventors:
# Inventor's Name Inventor's Address
1 RENE BERTOCCHIO 49 BIS,RUE DES VALLIERES, 69390VERNAISON
2 ANDRE LANTZ DOMAINE DE LA HETRAIE 69390 VERNAISON
3 LAURENT WENDLINGER 44,AVENUE DE GENERAL DA GAULLE 69230 SAINT GENIS LAVAL
PCT International Classification Number C07C17/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 96 01214 1996-02-01 France