USRE29044E - Method for the preparation of acetyl chloride - Google Patents
Method for the preparation of acetyl chloride Download PDFInfo
- Publication number
- USRE29044E USRE29044E US05/662,447 US66244776A USRE29044E US RE29044 E USRE29044 E US RE29044E US 66244776 A US66244776 A US 66244776A US RE29044 E USRE29044 E US RE29044E
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- United States
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- reaction
- chcl
- acetyl chloride
- chlorine
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- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000012346 acetyl chloride Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 22
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- -1 chlorine radicals Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
Definitions
- This invention relates to a method for the preparation of acetyl chloride, and more particularly to a method for preparing acetyl chloride by interacting 1,1-dichloroethane (hereinafter referred to simply as 1,1-DCE) and chlorine and oxygen under the irradiation of light.
- 1,1-DCE 1,1-dichloroethane
- acid chlorides are very reactive and useful as an esterifying agent or an acylating agent.
- acetyl chloride is a compound which can be effectively used for introducing an acetyl group into other compounds.
- Acetyl chloride has been usually prepared by a method wherein acetic acid is chlorinated by means of a particular chlorinating agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride or phosgene.
- a particular chlorinating agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride or phosgene.
- the method using such chlorinating agent has drawbacks in that the chlorinating agents are relatively expensive and special care is required in handling them, and that a large amount of by-products are formed as a result of the chlorination reaction. Accordingly, it is not necessarily advantageous to conduct a chlorination reaction by the use of such method, particularly when acetyl chloride is to be produced on an industrial scale.
- the present invention there is provided a method for preparing acetyl chloride by photooxidizing 1,1-DCE in the presence of chlorine.
- the present invention is characterized by interacting 1,1-DCE and chlorine and oxygen under light-exposing conditions.
- 1,1-DCE which is used as a starting material in the present invention can be easily prepared, for example, by adding hydrogen chloride to vinyl chloride, thus being readily available at a low cost.
- 1,1-DCE when 1,1-DCE is subjected to reaction with a mixture of chlorine and oxygen under the influence of light, chlorine molecules dissociate by the action of light to give chlorine radicals.
- the chlorine radicals function to expel a hydrogen at 1-position of 1,1-DCE thereby forming 1,1-dichloroethyl radicals.
- the light irradiation used in the reaction of the present invention is essentially required to activate chlorine molecules.
- a light source used for the light irradiation should generate light having a wavelength smaller than about 5000 A, preferably in the range of 2000 A - 4500 A.
- the ratio of oxygen gas and chlorine gas existing in the reaction system should be maintained within a certain range so as to produce acetyl chloride at a suitable reaction velocity with a high yield.
- the ratio of oxygen to chlorine is desired to be within a range of 5:1 - 1:5, preferably 3:1 - 1:3.
- reaction temperatures it is desired to conduct the reaction at a temperature within a range of from room temperature to 200° C. preferably 20° - 100° C. since a remarkably high reaction temperature accelerates the decomposition of acetyl chloride formed.
- acetyl chloride can be prepared, in the present invention, by interacting 1,1-DCE and oxygen and chlorine in a feeding ratio of 5:1 - 1:5, preferably 3:1 - 1:3, with irradiation of light having a wavelength of smaller than about 5000 A, preferably a wavelength of 2000 A - 4500 A, at a temperature of from room temperature to 200° C, preferably 20° - 100° C.
- 1,1,1-trichloroethane is a useful compound in the sense that it can be suitably used as a solvent for various substances, or may be converted into acetyl chloride by hydrolysis as described in U.S. Pat. No. 1,870,601.
- the formation ratio of acetyl chloride and 1,1,1-trichloroethane can be freely varied with changes in the feeding ratio of chlorine and oxygen used in the reaction of the present invention. This will be particularly illustrated in Example 2 which will appear hereinafter.
- the reaction may be conducted either in a gas phase or a liquid phase since the boiling point of 1,1-DCE serving as a starting material is 57.3° C while the reaction temperature used is within a range of from room temperature to 200° C.
- a solvent such as carbon tetrachloride may be used.
- 1,1-DCE which is used as a starting material is not necessarily required to be pure, but may contain therein some amount of other compounds, including 1,2-dichloroethane, unsaturated compounds such as vinyl chloride, dichloroethylene, trichloroethylene, tetrachloroethylene, etc., and/or chlorine compounds as secondarily produced by the method of the present invention.
- acetyl chloride is not obstructed even if the reaction system includes inactive gases, which take no part in the reaction of the present invention, including nitrogen, carbon dioxide, and/or hydrogen chloride, in coexistence with chlorine and oxygen.
- the method of the present invention uses inexpensive and easily available 1,1-DCE as a starting material and acetyl chloride can be produced in a simple and easy manner, thus the present invention being capable of great contribution to chemical industries.
- a transparent pyrex glass reaction container which had a diameter of about 7 cm and an inner volume of about 100 ml with a flat top and bottom and which was equipped with a reflux condenser and with a gas inlet and a sampling outlet, was placed in a thermostat the temperature of which was controlled at 50° C. Then, 70 g of 1,1-DCE was introduced into the container and chlorine gas and oxygen gas were further charged to the container each in an amount of 0.1 mol/g under irradiation of a 100 W high pressure mercury lamp (type SHL-100uV produced by Toshiba K.K.) while agitating by means of an agitator having teflon (Registered Trade Mark) coated blades.
- a 100 W high pressure mercury lamp type SHL-100uV produced by Toshiba K.K.
- the composition of the reaction solution was changed with the reaction time, as shown in Table 1.
- Example 1 was repeated except that chlorine gas and oxygen gas were charged in various different ratios and the reaction was conducted for 2 hours.
- the reaction is shown in Table 2 below.
- Example 1 was repeated except that a mixture of 35 g of 1,1-DCE and 35 g of 1,2-DCE was used and the reaction time was 2 hours.
- the resultant reaction solution contained the following components.
- Example 1 was repeated except that a mixture of 35 g of 1,1-DCE and 35 g of cis-1,2-dichloroethylene was used with a reaction time of 2 hours.
- the resultant reaction solution contained the following components.
- a usual gas phase flow type photo-reactor was used as a reaction container and a lamp (type SHL - 100 UV) of an ultra-violet ray was used as a light source.
- 1,1-DCE was gasified with use of an evaporator.
- the gasified 1,1-DCE was mixed with chlorine gas and oxygen gas in such a manner that a mixing ratio of 1,1-DCE: Cl 2 : O 2 was 1:1:1 (by mole).
- the mixture gas was fed to the gas phase reactor of 90° C at such a flow rate that the residual time of the flowing gas was about 100 sec.
- the resultant gas discharged from the reactor was cooled and subjected to a test for determining components which were contained in the final gas.
- the test results are as follows.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a method for preparing acetyl chloride by reacting 1,1-dichloroethane with chlorine and oxygen under the irradiation of light.
Description
This invention relates to a method for the preparation of acetyl chloride, and more particularly to a method for preparing acetyl chloride by interacting 1,1-dichloroethane (hereinafter referred to simply as 1,1-DCE) and chlorine and oxygen under the irradiation of light.
In general, acid chlorides are very reactive and useful as an esterifying agent or an acylating agent. Among them, acetyl chloride is a compound which can be effectively used for introducing an acetyl group into other compounds.
Acetyl chloride has been usually prepared by a method wherein acetic acid is chlorinated by means of a particular chlorinating agent such as phosphorus pentachloride, phosphorus trichloride, thionyl chloride or phosgene. However, the method using such chlorinating agent has drawbacks in that the chlorinating agents are relatively expensive and special care is required in handling them, and that a large amount of by-products are formed as a result of the chlorination reaction. Accordingly, it is not necessarily advantageous to conduct a chlorination reaction by the use of such method, particularly when acetyl chloride is to be produced on an industrial scale.
It is therefore an object of the present invention to provide a method of the preparation of acetyl chloride by the use of inexpensive starting materials and an easy reaction process.
According to the present invention, there is provided a method for preparing acetyl chloride by photooxidizing 1,1-DCE in the presence of chlorine. In other words, the present invention is characterized by interacting 1,1-DCE and chlorine and oxygen under light-exposing conditions.
The present invention will be described in more detail.
1,1-DCE which is used as a starting material in the present invention can be easily prepared, for example, by adding hydrogen chloride to vinyl chloride, thus being readily available at a low cost. In accordance with the present invention, when 1,1-DCE is subjected to reaction with a mixture of chlorine and oxygen under the influence of light, chlorine molecules dissociate by the action of light to give chlorine radicals. The chlorine radicals function to expel a hydrogen at 1-position of 1,1-DCE thereby forming 1,1-dichloroethyl radicals. The light irradiation used in the reaction of the present invention is essentially required to activate chlorine molecules. A light source used for the light irradiation should generate light having a wavelength smaller than about 5000 A, preferably in the range of 2000 A - 4500 A.
Immediately after the formation of 1,1-dichloroethyl radicals, the addition reaction of chlorine molecules to the 1,1-dichloroethyl radicals and that of oxygen molecules to the 1,1-dichloroethyl radicals occur competitively. Accordingly, in order to increase the yield of acetyl chloride, it is necessary to increase the concentration of oxygen existing in the reaction system so that the reaction of the 1,1-dichloroethyl radicals occurs more easily with oxygen molecules occurs than with chlorine molecules. However, if the concentration of chlorine molecules in the reaction system is reduced to an extremely low level as compared with that of oxygen molecules, the formation of 1,1-dichloroethyl radicals will also decrease, with the result that a formation velocity of acetyl chloride which is obtained by the addition reaction between the radicals and oxygen molecules is remarkably lowered. In this sense, the ratio of oxygen gas and chlorine gas existing in the reaction system should be maintained within a certain range so as to produce acetyl chloride at a suitable reaction velocity with a high yield. Experiments revealed that the ratio of oxygen to chlorine is desired to be within a range of 5:1 - 1:5, preferably 3:1 - 1:3. With regard to reaction temperatures, it is desired to conduct the reaction at a temperature within a range of from room temperature to 200° C. preferably 20° - 100° C. since a remarkably high reaction temperature accelerates the decomposition of acetyl chloride formed.
As described hereinabove, acetyl chloride can be prepared, in the present invention, by interacting 1,1-DCE and oxygen and chlorine in a feeding ratio of 5:1 - 1:5, preferably 3:1 - 1:3, with irradiation of light having a wavelength of smaller than about 5000 A, preferably a wavelength of 2000 A - 4500 A, at a temperature of from room temperature to 200° C, preferably 20° - 100° C. Upon production of acetyl chloride under the above-mentioned conditions, there are also produced various by-products, including hydrogen chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, monochloroacetylchloride, 1,1,2,2-tetrachloroethane, 1,1,2-tetrachloroethane, etc. Hydrogen chloride can be removed immediately from the reaction system since the same exists in the form of gas. On the other hand, the by-products remaining in the reaction system can be also separated from acetyl chloride when the acetyl chloride is collected by fraction distillation in an usual manner. Furthermore, the by-products may also be respectively collected by an usual fraction distillation. Among them, 1,1,1-trichloroethane is a useful compound in the sense that it can be suitably used as a solvent for various substances, or may be converted into acetyl chloride by hydrolysis as described in U.S. Pat. No. 1,870,601. The formation ratio of acetyl chloride and 1,1,1-trichloroethane can be freely varied with changes in the feeding ratio of chlorine and oxygen used in the reaction of the present invention. This will be particularly illustrated in Example 2 which will appear hereinafter.
In accordance with the present invention, the reaction may be conducted either in a gas phase or a liquid phase since the boiling point of 1,1-DCE serving as a starting material is 57.3° C while the reaction temperature used is within a range of from room temperature to 200° C. Where the reaction is conducted in a liquid phase, a solvent such as carbon tetrachloride may be used.
1,1-DCE which is used as a starting material is not necessarily required to be pure, but may contain therein some amount of other compounds, including 1,2-dichloroethane, unsaturated compounds such as vinyl chloride, dichloroethylene, trichloroethylene, tetrachloroethylene, etc., and/or chlorine compounds as secondarily produced by the method of the present invention.
Moreover, the formation of acetyl chloride is not obstructed even if the reaction system includes inactive gases, which take no part in the reaction of the present invention, including nitrogen, carbon dioxide, and/or hydrogen chloride, in coexistence with chlorine and oxygen.
As is apparent from the foregoing, the method of the present invention uses inexpensive and easily available 1,1-DCE as a starting material and acetyl chloride can be produced in a simple and easy manner, thus the present invention being capable of great contribution to chemical industries.
The following specific embodiments are included in order to more fully describe the present invention. These embodiments are for purposes of exemplification only and in no way are intended to limit the scope of the invention.
A transparent pyrex glass reaction container which had a diameter of about 7 cm and an inner volume of about 100 ml with a flat top and bottom and which was equipped with a reflux condenser and with a gas inlet and a sampling outlet, was placed in a thermostat the temperature of which was controlled at 50° C. Then, 70 g of 1,1-DCE was introduced into the container and chlorine gas and oxygen gas were further charged to the container each in an amount of 0.1 mol/g under irradiation of a 100 W high pressure mercury lamp (type SHL-100uV produced by Toshiba K.K.) while agitating by means of an agitator having teflon (Registered Trade Mark) coated blades.
The composition of the reaction solution was changed with the reaction time, as shown in Table 1.
Table 1
__________________________________________________________________________
Changes in Composition of Reaction Solution with Elapses of Reaction
Time
Reaction
time Composition of Reaction Solution (mol %)
(min)
CH.sub.3 CHCl.sub.2
CH.sub.3 COCl
CH.sub.3 CCl.sub.3
CH.sub.2 ClCHCl.sub.2
CH.sub.2 ClCOCl
CH.sub.2 ClCCl.sub.3
CHCl.sub.2 CHCl.sub.2
CHCl.sub.2 COCl
__________________________________________________________________________
30 88.8 5.0 4.3 1.5 0.3 -- -- --
60 72.7 9.6 8.5 3.6 0.7 -- -- --
90 66.0 14.7 12.8 5.1 1.1 0.1 -- 0.1
120 51.1 22.1 17.6 7.1 1.7 0.2 -- 0.1
150 26.5 31.5 27.3 10.5 2.8 0.8 0.2 0.2
180 7.8 41.0 31.4 11.2 4.0 2.2 0.8 0.3
210 1.1 43.3 33.0 9.7 5.1 3.4 4.5 0.7
240 0.2 41.8 33.4 8.1 7.1 4.9 3.2 1.3
__________________________________________________________________________
Example 1 was repeated except that chlorine gas and oxygen gas were charged in various different ratios and the reaction was conducted for 2 hours. The reaction is shown in Table 2 below.
Table 2
__________________________________________________________________________
Influence by Varied Mixing Ratios of Chlorine and Oxygen
Charged Amount
Composition of Reaction Solution (mol %)
Cl.sub.2
O.sub.2
CH.sub.3 CHCl.sub.2
CH.sub.3 COCl
CH.sub.3 CCl.sub.3
CH.sub.2 ClCHCl.sub.2
CH.sub.2 ClCOCl
CH.sub.2 ClCCl.sub.3
CHCl.sub.2 CHCl.sub.2
CHCl.sub.2
__________________________________________________________________________
COCl
0.1 0.1 51.1 22.1 17.6 7.1 1.7 0.2 -- 0.1
0.2 0.1 25.3 19.5 34.5 13.8 4.2 1.3 1.2 0.2
0.1 0.2 64.2 23.7 9.3 1.5 1.3 -- -- --
0.3 0.1 17.3 15.2 41.6 18.1 2.1 3.7 2.0 --
0.1 0.3 70.1 27.1 1.5 -- 1.3 -- -- --
__________________________________________________________________________
70 g of 1,1-DCE was mixed with chlorine gas, oxygen gas and nitrogen gas which were fed at 0.1 mol/h, 0.1 mol/h and 0.2 mol/h, respectively, for reaction in the same manner as in Example 1. A composition of the reaction solution obtained after a lapse of 2 hours is as follows:
______________________________________
CH.sub.3 CHCl.sub.2
63.6 mol %
CH.sub.3 COCl
16.5
CH.sub.3 CCl.sub.3
13.1
CH.sub.2 ClCHCl.sub.2
5.2
CH.sub.2 ClCOCl
1.4
CH.sub.2 ClCCl.sub.3
0.1
CHCl.sub.2 CHCl.sub.2
0.1
CHCl.sub.2 COCl
--
______________________________________
Example 1 was repeated except that a mixture of 35 g of 1,1-DCE and 35 g of 1,2-DCE was used and the reaction time was 2 hours. The resultant reaction solution contained the following components.
______________________________________
CH.sub.3 CHCl.sub.2
21.7 mol %
CH.sub.2 ClCH.sub.2 Cl
40.7
CH.sub.3 COCl
12.1
CH.sub.3 CCl.sub.3
9.6
CH.sub.2 ClCHCl.sub.2
12.4
CH.sub.2 ClCOCl
3.4
CH.sub.2 ClCCl.sub.3
0.1
CHCl.sub.2 CHCl.sub.2
--
CHCl.sub.2 COCl
0.1
______________________________________
Example 1 was repeated except that a mixture of 35 g of 1,1-DCE and 35 g of cis-1,2-dichloroethylene was used with a reaction time of 2 hours. The resultant reaction solution contained the following components.
______________________________________
CH.sub.2 CHCl.sub.2
27.0 mol %
cis--CHCl=CHCl
13.6
CH.sub.3 COCl
12.1
CH.sub.3 CCl.sub.3
6.8
CH.sub.2 ClCHCl.sub.2
4.2
CH.sub.2 ClCOCl
1.7
CH.sub.2 ClCCl.sub.3
0.1
CHCl.sub.2 CHCl.sub.2
13.3
CHCl.sub.2 COCl
0.8
CHCl.sub.2 CHO
0.2
______________________________________
A usual gas phase flow type photo-reactor was used as a reaction container and a lamp (type SHL - 100 UV) of an ultra-violet ray was used as a light source. While, 1,1-DCE was gasified with use of an evaporator. The gasified 1,1-DCE was mixed with chlorine gas and oxygen gas in such a manner that a mixing ratio of 1,1-DCE: Cl2 : O2 was 1:1:1 (by mole). The mixture gas was fed to the gas phase reactor of 90° C at such a flow rate that the residual time of the flowing gas was about 100 sec. The resultant gas discharged from the reactor was cooled and subjected to a test for determining components which were contained in the final gas. The test results are as follows.
______________________________________
CH.sub.3 CHCl.sub.2
47.3 mol %
CH.sub.3 COCl
28.3
CH.sub.3 CCl.sub.3
12.3
CH.sub.2 ClCHCl.sub.2
6.8
CH.sub.2 ClCOCl
3.6
CH.sub.2 ClCCl.sub.3
0.3
CHCl.sub.2 CHCl.sub.2
0.4
CHCl.sub.2 COCl
0.8
CHCl.sub.2 CCl.sub.3
0.2
______________________________________
Claims (6)
1. A method for the preparation of acetyl chloride characterized by interacting 1,1-dichloroethane and chlorine gas and oxygen gas under light irradiated conditions.
2. A method according to claim 1, wherein oxygen gas and chlorine gas are fed in a ratio within a range of 5:1 - 1:5.
3. A method according to claim 1, wherein the reaction is conducted with the use of light having a wavelength smaller than 5000 A.
4. A method according to claim 3, wherein said wavelength is within a range of 2000 - 4500 A.
5. A method according to claim 1, wherein the reaction is conducted at a temperature of from room temperature to 200° C.
6. A method according to claim 5, wherein said temperature is within a range of 20° - 100° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/662,447 USRE29044E (en) | 1972-08-19 | 1976-03-01 | Method for the preparation of acetyl chloride |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8322272A JPS523366B2 (en) | 1972-08-19 | 1972-08-19 | |
| JA47-83222 | 1972-08-19 | ||
| US389311A US3894921A (en) | 1973-08-17 | 1973-08-17 | Method for the preparation of acetyl chloride |
| US05/662,447 USRE29044E (en) | 1972-08-19 | 1976-03-01 | Method for the preparation of acetyl chloride |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US389311A Reissue US3894921A (en) | 1972-08-19 | 1973-08-17 | Method for the preparation of acetyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29044E true USRE29044E (en) | 1976-11-23 |
Family
ID=27304157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/662,447 Expired - Lifetime USRE29044E (en) | 1972-08-19 | 1976-03-01 | Method for the preparation of acetyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29044E (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1983004410A1 (en) * | 1982-06-07 | 1983-12-22 | The Dow Chemical Company | Selective photochlorination of 1,1-dichloroethane with iodine catalyst |
| US5259938A (en) * | 1992-09-15 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for omega-halo-perfluoro acid chlorides |
| EP0659729A1 (en) * | 1993-12-23 | 1995-06-28 | Solvay Fluor und Derivate GmbH | Process for preparing chlorides of polyfluorochloro- and perfluoro carboxylic acids in the presence of chlorine |
| US5545298A (en) * | 1993-08-13 | 1996-08-13 | Solvay Fluor Und Derivate Gmbh | Process for preparing polyfluorocarboxylic acid chlorides and perfluorocarboxylic acid chlorides |
-
1976
- 1976-03-01 US US05/662,447 patent/USRE29044E/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Hazeldine et al., Chemical Society Journal (London), (1955) pp. 2151 to 2163 * |
| hazeldine et al., Chemical Society Journal (London), (1955) pp. 2151 to 2163. |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1983004410A1 (en) * | 1982-06-07 | 1983-12-22 | The Dow Chemical Company | Selective photochlorination of 1,1-dichloroethane with iodine catalyst |
| US5259938A (en) * | 1992-09-15 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Process for omega-halo-perfluoro acid chlorides |
| US5545298A (en) * | 1993-08-13 | 1996-08-13 | Solvay Fluor Und Derivate Gmbh | Process for preparing polyfluorocarboxylic acid chlorides and perfluorocarboxylic acid chlorides |
| EP0659729A1 (en) * | 1993-12-23 | 1995-06-28 | Solvay Fluor und Derivate GmbH | Process for preparing chlorides of polyfluorochloro- and perfluoro carboxylic acids in the presence of chlorine |
| US5569782A (en) * | 1993-12-23 | 1996-10-29 | Solvay Fluor Und Derivate Gmbh | Process for preparing polyfluorochlorocarbonyl chlorides and perfluorocarbonyl chlorides with addition of chlorine |
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