GB2082180A - Process of preparing hexachloroacetone using phosphine catalyst to complete chlorination - Google Patents
Process of preparing hexachloroacetone using phosphine catalyst to complete chlorination Download PDFInfo
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- GB2082180A GB2082180A GB8124769A GB8124769A GB2082180A GB 2082180 A GB2082180 A GB 2082180A GB 8124769 A GB8124769 A GB 8124769A GB 8124769 A GB8124769 A GB 8124769A GB 2082180 A GB2082180 A GB 2082180A
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- Prior art keywords
- phosphine
- hexachloroacetone
- process according
- acetone
- chlorine
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 26
- 238000005660 chlorination reaction Methods 0.000 title abstract description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 41
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000012808 vapor phase Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 4
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 3
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical group PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- RVSIFWBAGVMQKT-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropan-2-one Chemical compound ClC(Cl)C(=O)C(Cl)(Cl)Cl RVSIFWBAGVMQKT-UHFFFAOYSA-N 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical class CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- IZAMGZXBYPKBJL-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.C(CCC)P(CCCC)CCCC Chemical compound N1=CC=CC2=CC=CC=C12.C(CCC)P(CCCC)CCCC IZAMGZXBYPKBJL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- VEFOQWXHKLHKPX-UHFFFAOYSA-N diphenylphosphane quinoline Chemical compound N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)PC1=CC=CC=C1 VEFOQWXHKLHKPX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- AKICECWDRFGXGN-UHFFFAOYSA-N pyridine triphenylphosphane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 AKICECWDRFGXGN-UHFFFAOYSA-N 0.000 description 1
- MEMHXMMYIQUEDH-UHFFFAOYSA-N quinoline triphenylphosphane Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.N1=CC=CC2=CC=CC=C12 MEMHXMMYIQUEDH-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 tri-n-butylphosphine tri-n-butylamine Chemical compound 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
First, a mixture of lower chlorinated acetones having 2 to 2.5 chlorine atoms per molecule on the average is prepared in a state absorbed in an organic liquid. The lower chlorinated acetones are further chlorinated to hexachloroacetone by the addition of chlorine gas to the liquid, which is heated up to about 150 DEG C, by using either a phosphine or a combination of a phosphine and an amine as a chlorination catalyst. Preferably, acetone is initially chlorinated by vapor phase contact reaction with excess chlorine at 70-100 DEG C to the extent of 1.6- to 1.8-chloroacetone, which is absorbed in the organic liquid together with unreacted chlorine to undergo further chlorination at 25-80 DEG C to the extent of 2- to 2.5-chloracetone. This process gives hexachloracetone very low in the contents of lower chlorinated acetones with good yield.
Description
SPECIFICATION
Process of preparing hexachloroacetone using phosphine catalyst to complete chlorination
This invention relates to a process of preparing hexachloroacetone by gradual chlorination of
acetone with chlorine gas.
Hexachloroacetone is an important industrial chemical. For example, hydrolysis of this compound
under an alkaline condition gives chloroform and trichloroacetic acid, and hexafluoroacetone is obtained
by substitution of fluorine for chlorine of hexachloroacetone. More broadly hexachloroacetone is useful
as an intermediate of various medicines and agricultural chemicais.
The preparation of hexachloroacetone by chlorination of acetone is known for long, and various
processes have been developed in the past several decades.
As a relatively recent proposal, the process according to T. Ambrus, Rev. Chim., Vol 14 (No. 9), 506-508 (1963) is to obtain hexachloroacetone through the steps of first preparing lower chlorinated acetones, which are mainly trichloroacetone, by parallel flow contact reaction between 1 mole of 'vaporized acetone and 3 moles of chlorine gas at 80-900C in a column packed with Raschig rings and
next making the lower chlorinated acetones react with excess chlorine at an elevated temperature of 150--1600C by using an activated carbon catalyst.From an industrial viewpoint, however, this process
is rather unfavorable because of an inevitable and considerable loss of the unreacted portion of acetone,
which has a high vapor pressure, at the initial vapor phase chlorination step and also because of the
need for a large excess of chlorine gas at the final chlorination step.
U.S. Patent No. 3,265,740 published in 1966 proposes to obtain hexachloroacetone through the
steps of first preparing lower chlorinated acetones by vapor phase reaction between 1 mole of acetone
added with pyridine and 2 moles of chlorine gas and then achieving further chlorination of the lower
chlorinated acetones in liquid phase containing a catalytic amount of pyridine by the addition of chlorine
gas. This process, too, suffers from the loss of the unreacted portion of the vaporized acetone. As
another disadvantage, the product of this process tends to contain a considerable amount of 1,1,1
trichloroacetone because this specific trichloride is less susceptive to the effect of pyridine used as
chlorination catalyst than dichloroacetones and trichloroacetones of the other forms.
Japanese Patent Application Primary Publication No. 49 (1 974) -- 24909 proposes a three-stage
chlorination processor the preparation of hexachloroacetone. The initial stage is liquid phase
chlorination of acetone at a relatively low temperature. Resultant lower chlorinated acetones are further
chlorinated with heating in the presence of an organic base such as pyridine or its salt to the extent of 3
to 4.5 chlorine atoms per molecule on the average. At the final stage, the lower chlorinated acetones
are made to react with additional chlorine in the presence of the aforementioned organic base as
catalyst with application of heat and irradiation of actinic rays. An advantage of this process is that the
chlorination can be completed in a relatively short period of time and at relatively low temperatures.
However, there is a strong possibility of side-reactions during the first stage chlorination by reason of
contact between acetone and hydrogen chloride in the liquid phase reaction system and, besides, the
irradiation of actinic rays at the final stage chlorination offers intricacy and troublesomeness to the
construction and maintenance of the apparatus. Therefore, it is doubtful whether this process is
industrially profitable.
It is an object of the present invention to provide a novel process of efficiently preparing high
purity hexachloroacetone with good yield.
A primary feature of the present invention is to use a phosphine except triphenylphosphine as a
catalyst for liquid phase chlorination of lower chlorinated acetones to hexachloroacetone.
By a process according to the invention, hexachloroacetone is prepared through the steps of first
preparing a mixture of lower chlorinated acetones having 2 to 2.5 chlorine atoms per molecule on the
average in a state absorbed in an organic liquid medium, and then further chlorinating the lower
chlorinated acetones to hexachioroacetone by introducing chlorine gas into the liquid medium
containing the lower chlorinated acetones in the presence of a catalyst, which comprises a phosphine
except triphenylphosphine, while the liquid medium is kept heated in the temperature range from 600C
to 1500C.
A phosphine alone can be used as the catalyst,but alternatively and rather preferably a mixture of
a phosphine (except triphenylphosphine) and an organic base typified by an amine may be used.
It is recommended to prepare the aforementioned lower chlorinated acetones through the steps of
first preparing a very lower chlorinated acetones having 1.6 to 1.8 chlorine atoms per molecule on the
average by vapor contact reaction between acetone and excess chlorine gas, and allowing an organic
liquid medium to absorb the product of this vapor phase reaction and the residual reactants and
maintaining the resultant liquid phase reaction system at a temperature in the range from 25 to 800C to
thereby further chlorinate the very lower chlorinated acetones to the extent of 2 to 2.5 chlorine atoms
per molecule on the average.
It is convenient to use either hexachloroacetone or a lower chloroacetone as the organic liquid
medium, though not limitative.
The chlorination process according to the invention can readily be performed at relatively low
temperatures and gives hexachloroacetone very low in the contents of trichloroacetone and pentachloroacetone. By preparing the lower chlorinated acetones in the recommended way, both the purity of hexachloroacetone and the yield on the basis of acetone can remarkably be improved.
A process according to the invention can be performed either batch-wise or continuously.
An essential point of the present invention is to use a phosphine, either singly or jointly with an organic base, as a catalyst for chlorination of lower chlorinated acetones in an organic solvent to hexachloroacetone. Various phosphines except triphenylphosphine are of use for this purpose.
Monophenylphosphine, diphenylphosphine, dimethylphenylphosphine, triethylphosphine, tris(4methylphenyl)-phosphine, tri-n-butylphosphine and tri-n-octylphosphine can be named as examples of suitable phosphines. in the case of using a phosphine alone as the catalyst, a suitable quantity of the phosphine falls in the range from 0.1 to 5.0 mole%, and preferably from 0.2 to 1.0 mole%, of the total of the lower chlorinated acetones. The use of more than 5 mole% of phosphine is unfavorable from an economical viewpoint. If the quantity of the phosphine is less than 0.1 mole%, the product will become relatively low in purity and relatively high in the content of pentachloroacetone.
We have found and confirmed that the quantity of the phosphine employed as the catalyst can be reduced by using a suitable quantity of an amine or its salt jointly with the phosphine. However, it is impermissible to replace the entire quantity of phosphine by an amine because it results in the presence of a considerably large amount of 1,1,1 -trichloroacetone in the product. It is suitable to use an amine good at thermal stability and relatively high in boiling point. Examples of preferable compounds are pyridine, quinoline, n-tributylamine and n-trioctylamine. It is suitable that each of the phosphine and the jointly used amine amounts to 0.05-2.0 mol%, and preferably 0.1-0.5 mole%, of the total of the lower chlorinated acetones.
The catalyst may be added to the organic liquid medium after absorption of the lower chlorinated acetones, but it is permissible and raises no problem that the addition of the catalyst precedes the absorption of the lower chlorinated acetones in the organic liquid medium. A liquid catalyst such as trin-butylphosphine can directiy be poured into the organic liquid medium. A solid catalyst such as tris(4methylphenyl)phosphine would be introduced into the liquid medium as a solution in, for example, a lower chlorinated acetone. In the case of jointly using a phosphine and an amine, it makes no difference whether these two catalytic materials are added separately or mixed with each other in advance.
As to the organic liquid medium, it is convenient and preferable to use either hexachloroacetone or a lower chlorinated acetone. In the case of using a different solvent, it is important to select a solvent that does not influence the intended chlorination reaction, is relatively low in vapor pressure and can easily be separated from hexachloroacetone. Examples of useful solvents are carbon tetrachloride, chlorobenzene and trichlorotrifluoroethane. In any case a suitable quantity of the organic liquid medium falls in the range from 10 to 100 mol%, and preferably from 20 to 50 mole%, of the total of the lower chlorinated acetones to be absorbed.
The organic liquid medium or absorbent is used mainly because of a possibility of efficiently collecting the lower chlorinated acetones and also because of a possibility of moderating the thermal load on a reflux condenser that needs to be provided above the apparatus for the liquid phase chlorination, and further because of a contribution to the enhancement of the conversion of chlorine. - - The final stage chlorination of the lower chlorinated acetones to hexachloroacetone is accomplished by heating the liquid containing the lower chlorinated acetones and the catalyst to a temperature above 600 C, then starting the introduction of chlorine gas into the liquid at a suitable rate and gradually raising the temperature of the liquid up to about 1 500C while chlorine gas is continuously introduced.Where the catalyst is used in a relatively large quantity, it will be sufficient to heat the liquid to about 1400C. A practically complete chlorination of the lower chlorinated acetones to hexachloroacetone can be achieved by using a theoretical quantity or a slightly larger quantity of chlorine. The chlorination reaction proceeds almost stoichiometrically during an initial stage of the operation, but the rate of reaction tends to lower as the chlorination approaches completion. Therefore, at a later stage of this operation the rate of introduction of chlorine gas may be reduced to thereby avoid a large waste of chlorine.
The presence of water in the reaction system is undesirable because water exerts a poisoning effect on the phosphine catalyst and also because the presence of water accelerates corrosion of the reaction apparatus. In practice, however, there occurs no serious problem so long as the quantity of water in the reaction system is below about 0.25% by weight of acetone.
The best way of preparing lower chlorinated acetones having 2 to 2.5 chlorine atoms per molecule on the average is to first chlorinate acetone to the extent of 1.6 to 1.8 chlorine atoms per molecule on the average by vapor phase contact reaction between acetone and chlorine in a proportion of 1:2 to 1:3 by mole, followed by absorption of the thus chlorinated acetone and the unreacted portion of chlorine in an organic liquid medium, and maintain the resultant liquid reaction system in a moderately heated state for some period of time to allow further reaction between the chlorine and chloroacetone absorbed in the liquid medium. The reason for accomplishing the initial stage of chlorination in vapor phase is to avoid side-reactions that will give undesirable by-products such as phorone and/or mesityl oxide. The vapor phase reaction is performed as a parallel flow contact reaction at a reaction temperature in the range from 70 to 1000C. It is possible to determine the contact time within a relatively wide range such as from 5 to 20 seconds taking into consideration that the chlorination still
proceeds in the organic liquid medium.
In the liquid phase reaction for chlorination of the 1.6- to 1.8-chloroacetone to 2-to 2.5
chloroacetone, it is desirable to maintain the liquid phase reaction system at a temperature in the range from 25 to 800C from the viewpoint of enhancing the conversion of chlorine and minimizing the loss of
the organic materials.
EXAMPLE 1
Through a vaporizer, acetone was introduced into a horizontally heid reaction tube of glass (21 mm in inner diameter and 270 mm in length) at a constant rate of 0.36 mole/hr. Simultaneously and in the same direction chlorine gas was passed through the reaction tube at a constant rate of 0.9 mole/hr so that the mole ratio of acetone to chlorine was 1 :2.5, while the reaction tube was heated by an electric heater to maintain the interior of the tube at 70--800C to thereby cause parallel flow contact reaction between the acetone vapor and chlorine gas.The outlet of the reaction tube was connected to a 500 ml four-neck flask, which contained 1 50 g (0.57 moles) of hexachloroacetone and was equipped with an upper reflux condenser cooled at -5 to 0 C to maintain the temperature of the hexachloroacetone at 50-700C. The feed of acetone and chlorine into the reaction tube was continued for 2 hours and 47 minutes, so that the total quantity of acetone reached 1.0 mole.
The degree of chlorination of a mixture of lower chlorinated acetones formed by the vapor phase contact reaction and further chlorinated in the heated hexachloroacetone was confirmed to be 2.5 chlorine atoms per molecule on the average by quantitative analysis of hydrogen chloride obtained as a by-product and by gas chromatography analysis of the product.
To the liquid reaction system containing the lower chlorinated acetones absorbed in hexachloroacetone, 0.4 g of tri-n-butylphosphine (0.2 mole% of the total quantity of acetone introduced into the reaction tube) was added as a catalyst. Thereafter, the temperature of the liquid reaction system was brought to 600 C, and started was the introduction of chlorine gas into the liquid reaction system at a rate of 1.0 mole/hr. The temperature of the liquid reaction system was gradually raised up to 1 460C, and the introduction of chlorine gas was continued for 3.7 hr.
This process gave a crude hexachloroacetone of a light yellow color. Quantitative analysis by gas chromatography revealed that this crude hexachloroacetone had a purity of 95.4% and contained 0.2% of 1,-1,1 -trichloroacetone and 4.4% of pentachloroacetone. The total yield of hexachloroacetone based on acetone was 91.2%, excluding hexachloroacetone used as the absorbent.
REFERENCE 1
Generally in accordance with Example 1, 1.0 mole of acetone was chlorinated to the extent of 2.5 chlorine atoms per molecule on the average. As a minor modification, the quantity of hexachloroacetone used as absorbent was decreased to 100 g (0.38 moles).
In the final stage chlorination, 0.3 g of quinoline alone was used as the catalyst. The temperature of the liquid reaction system at the start of the introduction of chlorine gas (1.0 mole/hr) was 700C and gradually raised up to 14400. The introduction of chlorine gas was continued for 3.6 hours. crude hexachloroacetone obtained in this experiment had a purity of 94.7% and contained 4.2% of trichloroacetone and 1.1% of pentachloroacetone. The yield of hexachloroacetone based on acetone was 91.1%.
REFERENCE 2
The procedure of Reference 1 was repeated generally similarly, but 0.3 g of pyridine was used as the catalyst in the final stage chlorination in place of quinoline in Reference 1. As an additional modification, the liquid reaction system was heated up to 1460C.
A crude hexachloroacetoneobtained in Reference 2 had a purity of 94.4% and contained 5.3% of trichloroacetone and 0.3% of pentachloroacetone. The yield of hexachloroacetone based on acetone was 86.1%.
EXAMPLE 2
Generally in accordance with Example 1, 1.0 mole of acetone was chlorinated to the extent of 2.3 chlorine atoms per molecule on the average.
After the addition of 1.12 g of diphenylphosphine (0.6 mole% of the total of the lower chlorinated acetones) to the liquid reaction system, 4.4 inoles of chlorine gas was introduced into the liquid reaction system in 5.75 hr, while the reaction system was gradually heated from an initial temperature of 700C to a maximal temperature of 1490C.
Hexachloroacetone obtained in this example was colorless and transparent and had a purity of 6.1 %. The yield of hexachloroacetone based on acetone was 90.2%.
EXAMPLES 3 TO 8
In these Examples, the chlorination of 1.0 mole of acetone to the extent of 2.5 chlorinate atoms per molecule on the average was accompiished in accordance with Example 1, except that the quantity of hexachloroacetone used as the absorbent was decreased to 100 g.
The lower chlorinated acetones in the liquid phase were chlorinated to hexachloroacetone by the procedure of Example 1, but in each of Examples 3-8 a combination of a phosphine (0.1 mole) and an amine (0.1 mole) was used as the chlorination catalyst. In every Example chlorine gas was introduced into the heated liquid reaction system for a period of 3.6 hr at a rate of 1.0 mole/hr, but the initial and maximal temperatures of the reaction system were slightly different from example to example. The catalysts and the reaction temperatures in Examples 3-8 are shown in the following Table together with the results of the analysis of the products and the yields of hexachloroacetone.
Analysis trichloro- pentach loro- hexachloro acetone acetone acetone Yield Example 3 triphenylphosphine quinoline 2.1% 0.4% 97.5% 93.8% 80--142"C Example 4 triphenylphosphine pyridine 2.3% 0.4% 97.3% 91.2% 70--142"C Example 5 tri-n-butylphosphine quinoline 0.9% 0.3% 98.8% 89.2% 70-1440C Example 6 trill-butylphosphine pyridine - . 0.7% 0.3% 99.0% 94.5% 70-145"C Example 7 tri-n-butylphosphine tri-n-butylamine 0.4% 1.5% 98.1% 93.5% 70-146 0C Example 8 diphenylphosphine quinoline 1.4% 1.8% 96.8% 90.5% 70-150"C
Claims (12)
1. A process of preparing hexachloroacetone, comprising the steps of:
preparing a mixture of lower chlorinated acetones having 2 to 2.5 chlorine atoms per molecule on the average in a state absorbed in an organic liquid medium: and
chlorinating said lower chlorinated-acetone to hexachloroacetone by introducing chlorine gas into the liquid medium containing said lower chlorinated acetones in the presence of a catalyst which comprises a phosphine, except triphenylphosphine, while the liquid reaction system is kept heated in the temperature range from 600C to 1 500 C.
2. A process according to Claim 1, wherein said mixture of lower chlorinated acetones is prepared by the sub-steps of first chlorinating acetone to the extent of 1.6 to 1.8 chlorine atoms per molecule on the average by a vapor phase parallel flow contact reaction between acetone and chlorine at a temperature in the range from 70 to 1000C, the mole ratio of acetone to chlorine subjected to reaction being in the range from 1:2 to 1:3; allowing an organic liquid medium to absorb the product of said vapor phase contact reaction and the residual reactants; and maintaining a resultant liquid phase reaction system at a temperature in the range from 25 to 800C.
3. A process according to Claim 1 or 2, wherein said catalyst is said phosphine alone and amounts to 0.1 to 5.0 mole% of the total of said lower chlorinated acetones.
4. A process according to Claim 3, wherein said phosphine is selected from monophenylphosphine, diphenylphosphine, dimethylphenylphosphine, triethylphosphine, tris(4methylphenyl)phosphine, tri-n-butylphosphine and tri-n-octylphosphine.
5. A process according to Claim 1 or 2, wherein said catalyst consists of said phosphine and an organic base.
6. A process according to Claim 5, wherein said organic base is an amine, each of said phosphine and said amine amounting to 0.05 to 2.0 mole% of the total of said lower chlorinated acetones.
7. A process according to Claim 6, wherein said phosphine is selected from monophenylphosphine, diphenylphosphine, dimethylphenylphosphine, triethylphosphine, tris(4methylphenyl)phosphine, tri-n-butylphosphine and tri-n-octyiphosphine, said amine being selected from the group consisting of pyridine, quinoline, n-tributylamine and n-trioctylamine.
8. A process according to Claim 2, wherein said organic liquid medium amounts to 10 to 100 mole% of the total of said lower chlorinated acetones.
9. A process according to Claim 8, wherein said organic liquid medium is hexachloroacetone.
10. A process according to Claim 8, wherein said organic liquid medium is a chlorinated acetone.
11. A process according to Claim 8, wherein said organic liquid medium is selected from carbon tetrachloride, chlorobenzene and trichlorotrifl uoroethane.
12. A process of preparing hexachloroacetone substantially as herein described in any one of
Examples 1 to 8.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11038680A JPS5735537A (en) | 1980-08-13 | 1980-08-13 | Preparation of hexachloroacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2082180A true GB2082180A (en) | 1982-03-03 |
| GB2082180B GB2082180B (en) | 1984-07-11 |
Family
ID=14534484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8124769A Expired GB2082180B (en) | 1980-08-13 | 1981-08-13 | Process of preparing hexachloroacetone using phosphine catalyst to complete chlorination |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5735537A (en) |
| DE (1) | DE3131895C2 (en) |
| FR (1) | FR2488602B1 (en) |
| GB (1) | GB2082180B (en) |
| IT (1) | IT1138147B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899482A (en) * | 2014-01-08 | 2016-08-24 | 旭硝子株式会社 | Production method for hexachloroacetone |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2218709B1 (en) | 2007-12-03 | 2014-03-19 | Asahi Glass Company, Limited | Method for producing carbonate compound |
| CN101883752B (en) | 2007-12-03 | 2014-07-30 | 旭硝子株式会社 | Method for producing carbonate compound |
| JPWO2011062104A1 (en) | 2009-11-17 | 2013-04-04 | 旭硝子株式会社 | Method for producing polycarbonate |
| EP2883861A4 (en) | 2012-08-10 | 2016-03-23 | Asahi Glass Co Ltd | Method for producing carbonate compound and method for producing aromatic polycarbonate |
| SG11201504395SA (en) | 2012-12-06 | 2015-07-30 | Asahi Glass Co Ltd | Method for producing carbonate compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635117A (en) * | 1949-05-12 | 1953-04-14 | Allied Chem & Dye Corp | Preparation of polychloroacetones |
| US3265740A (en) * | 1962-07-11 | 1966-08-09 | Du Pont | Process for chlorinating acetone and acetylacetone |
| US3988369A (en) * | 1974-09-26 | 1976-10-26 | Pearson Donald E | Process and reactant for halogenating organic compounds |
-
1980
- 1980-08-13 JP JP11038680A patent/JPS5735537A/en active Granted
-
1981
- 1981-08-11 IT IT23468/81A patent/IT1138147B/en active
- 1981-08-12 FR FR8115641A patent/FR2488602B1/en not_active Expired
- 1981-08-12 DE DE3131895A patent/DE3131895C2/en not_active Expired
- 1981-08-13 GB GB8124769A patent/GB2082180B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899482A (en) * | 2014-01-08 | 2016-08-24 | 旭硝子株式会社 | Production method for hexachloroacetone |
| US20160304428A1 (en) * | 2014-01-08 | 2016-10-20 | Asahi Glass Company, Limited | Production method for hexachloroacetone |
| US9745241B2 (en) | 2014-01-08 | 2017-08-29 | Asahi Glass Company, Limited | Production method for hexachloroacetone |
| CN105899482B (en) * | 2014-01-08 | 2019-01-22 | 旭硝子株式会社 | The manufacturing method of hexachloroacetone |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2488602B1 (en) | 1985-07-05 |
| FR2488602A1 (en) | 1982-02-19 |
| JPS5735537A (en) | 1982-02-26 |
| IT8123468A0 (en) | 1981-08-11 |
| IT1138147B (en) | 1986-09-17 |
| GB2082180B (en) | 1984-07-11 |
| DE3131895C2 (en) | 1984-10-31 |
| JPS6116255B2 (en) | 1986-04-28 |
| DE3131895A1 (en) | 1982-03-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |