CA1148980A - Process for the continuous manufacture of octachlorocyclopentene - Google Patents
Process for the continuous manufacture of octachlorocyclopenteneInfo
- Publication number
- CA1148980A CA1148980A CA000336137A CA336137A CA1148980A CA 1148980 A CA1148980 A CA 1148980A CA 000336137 A CA000336137 A CA 000336137A CA 336137 A CA336137 A CA 336137A CA 1148980 A CA1148980 A CA 1148980A
- Authority
- CA
- Canada
- Prior art keywords
- chlorine
- octachlorocyclopentene
- cyclopentadiene
- reaction
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract: of the Disclosure Process for the continuous manufacture of octachlorocyclopentene Process for the continuous manufacture of octa-chlorocyclopentene by a one-stage chlorination of cyclo-pentadiene in inert solvents and under elevated pressure.
Description
This invention relates to a process for the continuous manufacture of octachlorocyclopentene by a one-stage chlor-ination of cyclopentadiene in inert solvents and under ele-vated pressure. The reaction proceeds according to the 5 equation 5H6 + 7 Cl2 = CsCl8 ~ 6 HC]
Octachlorocyclopentene is used as intermediate for the manufacture of dyestuffs, plastic materials and insecti-cides. It is particularly suitable as starting material ;
for making hexachlorocyclopentadiene (cf. US-PS 2,742,506) which can be used for the manufacture of cyclodiene insec-ticides.
Since the first manufacture of octachlorocyclopentene in 1877, numerous ways of synthesis have been proposed of 15 which only the chlorination of aliphatic and cyclic C5-hydrocarbons has gained a certain industrial importance ?
(cf. Ungnade, McBee, Chem. Rev. 58, page 289 (1958)).
According to US-PS 2,714,124 chlorinated C5-hydrocar-bons having at least two chlorine atoms in the molecule 20 are reacted with chlorine on porous, surface-active cata-lysts at a temperature of from 280 to 500 C to give octa-chlorocyclopentene. Preferred starting compounds for this reaction are polychloropentanes having more than 5 chlorine atoms, which have to be prepared by photochlorination of 25 pentanes, for example by the process described in US-PS
Octachlorocyclopentene is used as intermediate for the manufacture of dyestuffs, plastic materials and insecti-cides. It is particularly suitable as starting material ;
for making hexachlorocyclopentadiene (cf. US-PS 2,742,506) which can be used for the manufacture of cyclodiene insec-ticides.
Since the first manufacture of octachlorocyclopentene in 1877, numerous ways of synthesis have been proposed of 15 which only the chlorination of aliphatic and cyclic C5-hydrocarbons has gained a certain industrial importance ?
(cf. Ungnade, McBee, Chem. Rev. 58, page 289 (1958)).
According to US-PS 2,714,124 chlorinated C5-hydrocar-bons having at least two chlorine atoms in the molecule 20 are reacted with chlorine on porous, surface-active cata-lysts at a temperature of from 280 to 500 C to give octa-chlorocyclopentene. Preferred starting compounds for this reaction are polychloropentanes having more than 5 chlorine atoms, which have to be prepared by photochlorination of 25 pentanes, for example by the process described in US-PS
2,473,162.
Another two-stage synthesis is described in US-PS
2,900,420 in which a product mixture defined as "tetra-chlorocyclopentane" is first produced by chlorination of cyclopentadiene in liquid phase at a temperature of ., .
.
from -50 to ~80 C, which mixture is then reacted with further ch]orine at temperatures rising from 170 to 275~ C
to give octachlorocyclopentene. By adding a catalyst, for example arsenic trioxide, the reaction time can be reduced from 39 hours to 11 hours with the use of 0.7 to 0.8 kg of tetrachlorocyclopentane. To increase the chlorinc concen-tration in the liquid phase pressures of up to 35 bar are recommended. In this patent specification it is expressly stated iII column 6, lines 30 to 64, that the reaction of cyclopentadiene with chlorine to give octachlorocyclopen-tene has to be carried out in two stages. The first reac-tion stage, i.e. the chlorination of cyclopentadiene to tetrachlorocyclopentane is strongly exothermal and, there-fore, the temperature has to be maintained below 80 C by cooling in order to avoid secondary reactions. This can be done without any adverse effect since the reaction proceeds very r~pidly even at a temperature of 0 C. As compar~d therewith, the chlorination of tetrachlorocyclopentane to octachlorocyclopentene takes place relatively slowly even at the initial boiling temperature of the organic mixture of 170 C. A combination of these two reaction stages, which have to be carried out at very different temperatures, for the purpose of a continuous manufacture of octachlorocyclo-pentene is difficuIt and expensive.
Another two-stage synthesis is proposed in US-PS
Another two-stage synthesis is described in US-PS
2,900,420 in which a product mixture defined as "tetra-chlorocyclopentane" is first produced by chlorination of cyclopentadiene in liquid phase at a temperature of ., .
.
from -50 to ~80 C, which mixture is then reacted with further ch]orine at temperatures rising from 170 to 275~ C
to give octachlorocyclopentene. By adding a catalyst, for example arsenic trioxide, the reaction time can be reduced from 39 hours to 11 hours with the use of 0.7 to 0.8 kg of tetrachlorocyclopentane. To increase the chlorinc concen-tration in the liquid phase pressures of up to 35 bar are recommended. In this patent specification it is expressly stated iII column 6, lines 30 to 64, that the reaction of cyclopentadiene with chlorine to give octachlorocyclopen-tene has to be carried out in two stages. The first reac-tion stage, i.e. the chlorination of cyclopentadiene to tetrachlorocyclopentane is strongly exothermal and, there-fore, the temperature has to be maintained below 80 C by cooling in order to avoid secondary reactions. This can be done without any adverse effect since the reaction proceeds very r~pidly even at a temperature of 0 C. As compar~d therewith, the chlorination of tetrachlorocyclopentane to octachlorocyclopentene takes place relatively slowly even at the initial boiling temperature of the organic mixture of 170 C. A combination of these two reaction stages, which have to be carried out at very different temperatures, for the purpose of a continuous manufacture of octachlorocyclo-pentene is difficuIt and expensive.
Another two-stage synthesis is proposed in US-PS
3,723,272. The first stage comprises the thermal splitting of dicyclopentadiene to give cyclopentadiene which is then reacted, after *ilution by chlorinated cyclopentanes,with an excess amount of chlorine, preferably at a temperature `
, ' ; ' ~ ' .
8g~30 o~ 60 to 1~0 C, with or without ultraviolet light, to give a polychlorocyclopentane having g or 5 chlorine atoms in the molecule. In the second stage this product is chlorin-ated at 160 C while being exposed to ultraviolet light to give octachloroeyclopentene.
The present invention provides a process or the con-tinuous manufacture of octachlorocyclopentene from cyclo-pentadiene and chlorine, whieh comprises combining eyclo-;
pentadiene, an inert diluent and an at least stoichiometric amount of chlorine under a pressure of 20 to 300 bar at temperatures of the three liquid components of at most 60 C
and limiting the maximum temperature of the following exo-thermal reaetion to 200 to 500 C.
The organic starting compound in the process of the invent'ion is eyelopentadiene. In prineiple eyelopentene and eyelopentane eouId also ~e used, but they are notavail-able as raw material in the s~me measure as cyclopentadiene and do not offer any advantage over eyelopentadiene.
Chlorine is used in an at least stoiehiometrie amount.
In order to avoid the formation of carbon black 110 to 800 %
of the stoichiometric ehlorine amount, preferably 110 to 400'%,and more preferably 110 to 200'%, will generally be - used.
- Cyelopentadiene is reaeted with ehlorine in the pre-senee of one or several diluents to avoid the formation of earbonization products in the strongly exothermal reaction.
The diluents should not react with cyclopentadiene since otherwise the yield of oetaehloroeyelopentene would be re-dueed and disturbing by-produets would be formed. The di-~., , . , ~ ,, .
. . ' ' . :, ~
' ' ' ":'.' ~ :'"-" ' ,' ,. . '' .: ' ,' ' ' , . : ~ ' ' .
. .
.
~IOE 78/F 194 luents should also be inert to chlorine in order not to in-crease the reaction entl1alpy set free and the chlorine de~
mand. Compounds that comply with these requirements are, for example perchlorinated hydrocarbons such as tetrachloro-methane and octachlorocyclopentene. The latter can be usedin pure form but also in the form of a crude product of the instant process substantially freed from chlorine, which is much more economical. The proportion by weight of diluent to cyclopentadiene is generally in the range of from 60 : 40 to 99 : 1, preferably 70 : 30 to 99 : 1, and more preferably 80 : 20 to 99 : 1.
Cyclopentadiene and the diluent are combined either individua]ly or in the form of a mixture, under a pressure of from 20 to 300 bar, with an at least stoichiometric amount of chlorine, all three components being in theliquid state and having a temperature of from their respective melting point to ~60 C. Cyclopentadiene tmelting point -97 C) and chlorine (melting point -101 C) are preferably used at a temperature of from -50 to +30 C, more prefer-ably -30 to ~10 C. These two components react spontane-ously with each other with heating of the reaction mixture to high temperatures. At a temperature above 500 C chloro-lysis of the C5-ring to tetrachloromethane, hexachloro-ethane and hexachlorobutadiene takes place to an increasing extent and, therefore, the temperature should not exceed 500 C anywhere in the reactor. On the other hand, it should not fall below 200 C at all places inside of the reactor.
To adjust the maximum temperature in the reactor in the range of from 200 to 500 C a sufficient excess of chlorine , ::
1~8~
is preferably used which acts as coolant. It is obvious, of course, that under otherwise identical conditions a higher chlorine excess is required to adjust a maximum ten-perature of 200 C than for adjusting a maximum temperature of 500 C. The total amount of chlorine used for reaction and cooling is at most 800 ~ of the stoichiometric amount.
Besides this adiabatic mode of operation, the surplus of reaction enthalpy can be transferred to an external cooling medium via a heat exchanger.
In the process of the invention catalysts and high energy radiation such as ultraviolet light need not be used.
Hence, no problems arise concerning the separation and re-generation of catalytically effective substances or the de-posit of carbon black on the windows of the light sources.
The reaction is carried out under a pressure of from 20 to 300 bar, a range o~ from 50 to 250 bar being prefer-red.
In spite of the dilution of the cyclopentadiene, a space-time-yield of up to 30 kg of octachlorocyclopentene is obtained per liter of reaction space and hour. Conse-~uently, a reactor having very small dimensions can be used for the continuous process of the invention.
In general, the selectivity for octachloro~ycloFentene is considerably above 90 %. Small amounts of tetrachlorome-~
thane, hexachloroethane, hexachlorobutadiene and hexachloro-benzene are formed as by-products but no chlorinated cyclo-pentadiene oligomers which, according to literature (cf.for example Burmakin et al., J. Appl. Chem. (UdSSR) 40, page 1536 (1967)), would have to be expected to a considerable ' ' : .
,- : :' : ' extent in the chlorination of cyclopentadiene in the liquid phase at a temperature above 50 C.
In contradistinction to the aforesaid multi-stage chlo-rination processes, in the process according to the inven-tion the total amount of hydrogen chloride resulting fromthe reaction of cyclopentadiene with chlorine is obtained in one stage and at elevated pressure. Hydrogen chloride can be separated more easily under elevated pressure and isolated in dry and pure form in which it can be further used directly in hydrochlorination or oxychlorination re-actions or inHCl electrolysis processes. Correspondingly, the excess of chlorine can be obtained under pressure in a form that is easy to liquefy and which can be used again without difficuIty for the chlorination of cyclopentadiene.
It is, therefore, preferred to work up the reaction mixture under ~levated pressure, although working up under atmos-pheric pressure is likewise possible.
The present process is thus excellently suitable for the continuous manufacture of octachlorocyclopentene from cyclopentadiene and chlorine. The advantages for a commer-cial use are especiaily the one-stage reaction, the very high space-time-yield and the relatively easy separation of the products obtained under pressure.
As reactor a high pressure tube with nickel lining proved to be suitable which is provided at the inlet side with a two substance nozzIe for the intense mixing of the reaction components. Other reactor designs and other mix-ing means are likewise possible.
The following examples illustrate the invention:
.
:' - . . . .
HOE 78/F 19~
E x a m p l e s The chl~rination of cyclopentadiene was carried out in a vertical high pressure tube of high temperature stainless steel and provided with a nickel lining. The tube had a length of 2200 mm, an outer diameter of 48 mm, an inner dia-meter of 25 mm and was closed at the ends with a nickel lens each. Prior to the beginning of the reaction the reactor was heated to an internal temperature of 200 C by means of
, ' ; ' ~ ' .
8g~30 o~ 60 to 1~0 C, with or without ultraviolet light, to give a polychlorocyclopentane having g or 5 chlorine atoms in the molecule. In the second stage this product is chlorin-ated at 160 C while being exposed to ultraviolet light to give octachloroeyclopentene.
The present invention provides a process or the con-tinuous manufacture of octachlorocyclopentene from cyclo-pentadiene and chlorine, whieh comprises combining eyclo-;
pentadiene, an inert diluent and an at least stoichiometric amount of chlorine under a pressure of 20 to 300 bar at temperatures of the three liquid components of at most 60 C
and limiting the maximum temperature of the following exo-thermal reaetion to 200 to 500 C.
The organic starting compound in the process of the invent'ion is eyelopentadiene. In prineiple eyelopentene and eyelopentane eouId also ~e used, but they are notavail-able as raw material in the s~me measure as cyclopentadiene and do not offer any advantage over eyelopentadiene.
Chlorine is used in an at least stoiehiometrie amount.
In order to avoid the formation of carbon black 110 to 800 %
of the stoichiometric ehlorine amount, preferably 110 to 400'%,and more preferably 110 to 200'%, will generally be - used.
- Cyelopentadiene is reaeted with ehlorine in the pre-senee of one or several diluents to avoid the formation of earbonization products in the strongly exothermal reaction.
The diluents should not react with cyclopentadiene since otherwise the yield of oetaehloroeyelopentene would be re-dueed and disturbing by-produets would be formed. The di-~., , . , ~ ,, .
. . ' ' . :, ~
' ' ' ":'.' ~ :'"-" ' ,' ,. . '' .: ' ,' ' ' , . : ~ ' ' .
. .
.
~IOE 78/F 194 luents should also be inert to chlorine in order not to in-crease the reaction entl1alpy set free and the chlorine de~
mand. Compounds that comply with these requirements are, for example perchlorinated hydrocarbons such as tetrachloro-methane and octachlorocyclopentene. The latter can be usedin pure form but also in the form of a crude product of the instant process substantially freed from chlorine, which is much more economical. The proportion by weight of diluent to cyclopentadiene is generally in the range of from 60 : 40 to 99 : 1, preferably 70 : 30 to 99 : 1, and more preferably 80 : 20 to 99 : 1.
Cyclopentadiene and the diluent are combined either individua]ly or in the form of a mixture, under a pressure of from 20 to 300 bar, with an at least stoichiometric amount of chlorine, all three components being in theliquid state and having a temperature of from their respective melting point to ~60 C. Cyclopentadiene tmelting point -97 C) and chlorine (melting point -101 C) are preferably used at a temperature of from -50 to +30 C, more prefer-ably -30 to ~10 C. These two components react spontane-ously with each other with heating of the reaction mixture to high temperatures. At a temperature above 500 C chloro-lysis of the C5-ring to tetrachloromethane, hexachloro-ethane and hexachlorobutadiene takes place to an increasing extent and, therefore, the temperature should not exceed 500 C anywhere in the reactor. On the other hand, it should not fall below 200 C at all places inside of the reactor.
To adjust the maximum temperature in the reactor in the range of from 200 to 500 C a sufficient excess of chlorine , ::
1~8~
is preferably used which acts as coolant. It is obvious, of course, that under otherwise identical conditions a higher chlorine excess is required to adjust a maximum ten-perature of 200 C than for adjusting a maximum temperature of 500 C. The total amount of chlorine used for reaction and cooling is at most 800 ~ of the stoichiometric amount.
Besides this adiabatic mode of operation, the surplus of reaction enthalpy can be transferred to an external cooling medium via a heat exchanger.
In the process of the invention catalysts and high energy radiation such as ultraviolet light need not be used.
Hence, no problems arise concerning the separation and re-generation of catalytically effective substances or the de-posit of carbon black on the windows of the light sources.
The reaction is carried out under a pressure of from 20 to 300 bar, a range o~ from 50 to 250 bar being prefer-red.
In spite of the dilution of the cyclopentadiene, a space-time-yield of up to 30 kg of octachlorocyclopentene is obtained per liter of reaction space and hour. Conse-~uently, a reactor having very small dimensions can be used for the continuous process of the invention.
In general, the selectivity for octachloro~ycloFentene is considerably above 90 %. Small amounts of tetrachlorome-~
thane, hexachloroethane, hexachlorobutadiene and hexachloro-benzene are formed as by-products but no chlorinated cyclo-pentadiene oligomers which, according to literature (cf.for example Burmakin et al., J. Appl. Chem. (UdSSR) 40, page 1536 (1967)), would have to be expected to a considerable ' ' : .
,- : :' : ' extent in the chlorination of cyclopentadiene in the liquid phase at a temperature above 50 C.
In contradistinction to the aforesaid multi-stage chlo-rination processes, in the process according to the inven-tion the total amount of hydrogen chloride resulting fromthe reaction of cyclopentadiene with chlorine is obtained in one stage and at elevated pressure. Hydrogen chloride can be separated more easily under elevated pressure and isolated in dry and pure form in which it can be further used directly in hydrochlorination or oxychlorination re-actions or inHCl electrolysis processes. Correspondingly, the excess of chlorine can be obtained under pressure in a form that is easy to liquefy and which can be used again without difficuIty for the chlorination of cyclopentadiene.
It is, therefore, preferred to work up the reaction mixture under ~levated pressure, although working up under atmos-pheric pressure is likewise possible.
The present process is thus excellently suitable for the continuous manufacture of octachlorocyclopentene from cyclopentadiene and chlorine. The advantages for a commer-cial use are especiaily the one-stage reaction, the very high space-time-yield and the relatively easy separation of the products obtained under pressure.
As reactor a high pressure tube with nickel lining proved to be suitable which is provided at the inlet side with a two substance nozzIe for the intense mixing of the reaction components. Other reactor designs and other mix-ing means are likewise possible.
The following examples illustrate the invention:
.
:' - . . . .
HOE 78/F 19~
E x a m p l e s The chl~rination of cyclopentadiene was carried out in a vertical high pressure tube of high temperature stainless steel and provided with a nickel lining. The tube had a length of 2200 mm, an outer diameter of 48 mm, an inner dia-meter of 25 mm and was closed at the ends with a nickel lens each. Prior to the beginning of the reaction the reactor was heated to an internal temperature of 200 C by means of
4 jacket heatings. Dilute cyclopentadiene and chlorine were introduced by means of membrane pumps in liquid form through a two substance nozzle at the lower end of the re-actor at the temperatures indicated in the following table.
The maximum internal temperature in the reactor was measur-ed by shifting a thermoelement in a stainless steel tube enclosed in a nickel tube (outer diameter 10 mm), which tube pro~ected from above into the reactor over a length of 2100 mm. The respective temperature was adjusted by variation of the amount of chlorine added. The jacket heatings were switched off as soon as the desired maximum internal reac- -tor temperature had been reached. At the upper end of the reactor the pressure of the products was released to atmo-spheric in a high pressure valve in order to determine the selectivities and space-time-y,ields of octachlorocyclopen-tene while renouncing the recovery of hydrogen chloride and chlorine. To this end the product mixture was passed into a separator cooled with a mixture of butanol and dry ice in which mainly hydrogen chloride and part of the chlorine were not condensed. The condensate was freed from chlorine by distillation and analyzed. The space-time-yields were . ~
:
, .
~89~30 calculated on a free reactor volume of 0.9 liter. No forma,ion o carbon black was observed.
. . .
'' :
, ~8980 N ~ N
C5~ ~ ' ' Ln a~ o u~ o t~
_ , - ~ S~
~0 ~0 ~ o o~ .' S . O O O O O O ' . U~ O O Lr) U~ o ~ ' ~) O O O O O O
.~ ~ 1 ., . .
~ ~ ~ .
. ~ ~ . ~ .
W~ ~ ' ,. .
m .Y ~ " er ,~
E-~ ~ ~ ~ er ~ ~ .
.
~d ~ ~ ~ 1~ oo O
el ~ ~d ~ a~ o ~ 3' : n. _ ~ S~
~1 ~ a ~ I O ~ = . . N I ~
~ ~ ~ r __ X
..... . . . .
. .
`
The maximum internal temperature in the reactor was measur-ed by shifting a thermoelement in a stainless steel tube enclosed in a nickel tube (outer diameter 10 mm), which tube pro~ected from above into the reactor over a length of 2100 mm. The respective temperature was adjusted by variation of the amount of chlorine added. The jacket heatings were switched off as soon as the desired maximum internal reac- -tor temperature had been reached. At the upper end of the reactor the pressure of the products was released to atmo-spheric in a high pressure valve in order to determine the selectivities and space-time-y,ields of octachlorocyclopen-tene while renouncing the recovery of hydrogen chloride and chlorine. To this end the product mixture was passed into a separator cooled with a mixture of butanol and dry ice in which mainly hydrogen chloride and part of the chlorine were not condensed. The condensate was freed from chlorine by distillation and analyzed. The space-time-yields were . ~
:
, .
~89~30 calculated on a free reactor volume of 0.9 liter. No forma,ion o carbon black was observed.
. . .
'' :
, ~8980 N ~ N
C5~ ~ ' ' Ln a~ o u~ o t~
_ , - ~ S~
~0 ~0 ~ o o~ .' S . O O O O O O ' . U~ O O Lr) U~ o ~ ' ~) O O O O O O
.~ ~ 1 ., . .
~ ~ ~ .
. ~ ~ . ~ .
W~ ~ ' ,. .
m .Y ~ " er ,~
E-~ ~ ~ ~ er ~ ~ .
.
~d ~ ~ ~ 1~ oo O
el ~ ~d ~ a~ o ~ 3' : n. _ ~ S~
~1 ~ a ~ I O ~ = . . N I ~
~ ~ ~ r __ X
..... . . . .
. .
`
Claims (3)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A single stage process for the continuous preparation of octachloro-cyclopentene in which cyclopentadiene in liquid form, an inert diluent and an at least stoichiometric amount of chlorine in liquid form are combined under a pressure of 20 to 300 bar and at temperatures of the three liquid components of at most 60°C
and the maximum temperature of the resultant exothermal reaction is limited to 200 to 500°C.
and the maximum temperature of the resultant exothermal reaction is limited to 200 to 500°C.
2. A process as claimed in claim 1, in which the maximum reaction temperature is adjusted by a suitable excess of chlorine.
3. A process as claimed in claim 1 in which the diluent is chloromethane or octachlorocyclopentene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2841237.5 | 1978-09-22 | ||
| DE19782841237 DE2841237A1 (en) | 1978-09-22 | 1978-09-22 | Octa:chloro-cyclopentene prodn. from cyclopentadiene - by continuous high-pressure chlorination at controlled temp. useful as intermediate for dyes, plastics and insecticides (NL 25.3.80) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148980A true CA1148980A (en) | 1983-06-28 |
Family
ID=6050118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000336137A Expired CA1148980A (en) | 1978-09-22 | 1979-09-21 | Process for the continuous manufacture of octachlorocyclopentene |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1148980A (en) |
| DE (1) | DE2841237A1 (en) |
| IL (1) | IL58289A (en) |
| NL (1) | NL7907067A (en) |
-
1978
- 1978-09-22 DE DE19782841237 patent/DE2841237A1/en not_active Withdrawn
-
1979
- 1979-09-20 IL IL58289A patent/IL58289A/en unknown
- 1979-09-21 NL NL7907067A patent/NL7907067A/en not_active Application Discontinuation
- 1979-09-21 CA CA000336137A patent/CA1148980A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IL58289A0 (en) | 1979-12-30 |
| NL7907067A (en) | 1980-03-25 |
| DE2841237A1 (en) | 1980-04-03 |
| IL58289A (en) | 1982-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |