GB1575853A - Process for the manufacture and separation of substituted thianthrenes - Google Patents
Process for the manufacture and separation of substituted thianthrenes Download PDFInfo
- Publication number
- GB1575853A GB1575853A GB3531077A GB3531077A GB1575853A GB 1575853 A GB1575853 A GB 1575853A GB 3531077 A GB3531077 A GB 3531077A GB 3531077 A GB3531077 A GB 3531077A GB 1575853 A GB1575853 A GB 1575853A
- Authority
- GB
- United Kingdom
- Prior art keywords
- substituted
- thianthrene
- complex
- process according
- solvent
- 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
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- 150000005029 thianthrenes Chemical class 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000926 separation method Methods 0.000 title description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 40
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 239000002879 Lewis base Substances 0.000 claims description 18
- 150000007527 lewis bases Chemical class 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- -1 perchloroethylene, trichloroethylene Chemical group 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- LQCSUVWASPTLDK-UHFFFAOYSA-N 1,2-dichloro-3,4-dimethylthianthrene Chemical compound S1C2=CC=CC=C2SC2=C1C(C)=C(C)C(Cl)=C2Cl LQCSUVWASPTLDK-UHFFFAOYSA-N 0.000 claims description 8
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XWTUFPFWNHRJNF-UHFFFAOYSA-N 1,2-dimethylthianthrene Chemical compound C1=CC=C2SC3=C(C)C(C)=CC=C3SC2=C1 XWTUFPFWNHRJNF-UHFFFAOYSA-N 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 2
- DGHKQBYAUUIYTD-UHFFFAOYSA-N 1-chloro-2,3-dimethylthianthrene Chemical compound S1C2=CC=CC=C2SC2=C1C=C(C)C(C)=C2Cl DGHKQBYAUUIYTD-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPRLNYBIJYFSNS-UHFFFAOYSA-K aluminum;thianthrene;trichloride Chemical group [Al+3].[Cl-].[Cl-].[Cl-].C1=CC=C2SC3=CC=CC=C3SC2=C1 BPRLNYBIJYFSNS-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XIGHKTWDPDTMFO-UHFFFAOYSA-N 1,2,3,4-tetramethylthianthrene Chemical class C1=CC=C2SC3=C(C)C(C)=C(C)C(C)=C3SC2=C1 XIGHKTWDPDTMFO-UHFFFAOYSA-N 0.000 description 1
- JGOMBFKQSKVEPN-UHFFFAOYSA-N 1,4,6,9-tetramethylthianthrene Chemical compound S1C2=C(C)C=CC(C)=C2SC2=C1C(C)=CC=C2C JGOMBFKQSKVEPN-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B49/00—Sulfur dyes
- C09B49/12—Sulfur dyes from other compounds, e.g. other heterocyclic compounds
- C09B49/124—Sulfur dyes from other compounds, e.g. other heterocyclic compounds from polycarbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
Description
(54) PROCESS FOR THE MANUFACTURE AND SEPARATION
OF SUBSTITUTED THIANTHRENES
(71) We, HOOKER CHEMICALS & PLASTICS CORP, a Corporation organised and existing under the laws of the State of New York, United States of America, of Niagara
Falls, State of New York, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to an improved process for the manufacture of substituted thianthrene compounds. Thianthrene and substituted thianthrenes are useful in a variety of chemical processes, for example, as chemical intermediates in the preparation of dyestuffs such as thianthrene vat dyes. In addition, various thianthrene compounds are useful plasticizers, pesticides, and flameproofing agents. Recently it has been found that substituted thianthrenes having electron withdrawing substituents, such as halogens, on the aromatic nuclei thereof are especially useful as components of catalyst systems for the directed nuclear chlorination of alkyl-benzenes. Although substituted thianthrenes have been known for many years, little effort has been directed toward the development of a process suitable for commercial manufacture.
In Specification No. 1456950 we describe and claim a method for the preparation of thianthrene which comprises the reaction of benzene with sulfur monochloride in the presence of aluminium chloride. The reaction product is a thianthrene aluminum chloride complex. The thianthrene may then be recovered from the complex by mixing the complex with an inert organic liquid to form a slurry, and treating the slurry with a Lewis base to free the thianthrene from said complex and to dissolve the thianthrene in the organic liquid. By this method thianthrene of high purity can be manufactured.
The present invention provides a process for separating a substituted thianthrene of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or fluorine, subject to the proviso that not all X's on each benzene ring are hydrogen from a complex thereof with aluminum chloride, which process comprises mixing the complex with an organic liquid which is a solvent for the substituted thianthrene but not for the complex or for aluminum chloride to form a slurry of the complex, and treating the slurry with a
Lewis base to which the organic liquid is inert to free the substituted thianthrene from the complex and to allow the substituted thianthrene to dissolve in the organic liquid.
The complex may be prepared as follows: Sulfur monochloride is added, preferably with stirring, to a stoichiometric excess of a substituted benzene compound of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or fluorine, subject to the proviso that not all X's are hydrogen in the presence of aluminum chloride, and reacted to form the complex. In this process, it is preferred that sulfur monochloride be added to the substituted benzene compound rather than the reverse, since the addition of the substituted benzene compound to sulfur monochloride may result in the formation of undesirable polymeric sulfur products. Furthermore, the addition of the sulfur monochloride is made slowly to prevent excessively brisk evolution of hydrogen chloride gas. To provide a reaction medium of suitable consistency for agitation and transfer through piping systems and to provide sufficient solvent for by-product sulfur, substituted diphenyl sulfides and reaction impurities it is important that a molar ratio of substituted benzene compound to sulfur monochloride be maintained at about 5.0 or higher. Higher ratios may be employed with no theoretical upper limit. However, the process of the present invention becomes somewhat less economical when the mole ratio of substituted compound to sulfur monochloride is greater than about 12.0 due to the necessity of handling excessively large volumes of liquid. The preferred mole ratio of substituted benzene compound to sulfur monochloride is between 6:1 and 8:1.
The thianthrene compounds prepared in accordance with this invention are described hereinbelow in accordance with the current Chemical Abstracts system whereby the numbering of ring positions is as follows:
The amount of aluminum chloride present may vary considerably. However, we have found that maximum yields of the substituted thianthrene and minimum production of by-product substituted diphenyl sulfide are achieved when aluminum chloride is present in a mole ratio of aluminum chloride; sulfur monochloride of between 0.4:1 and 1.6:1. At lower ratios the yield of the substituted thianthrene is substantially lowered. At higher ratios, the yield of the substituted thianthrene is lowered and the production of substituted diphenyl sulfide is increased. The temperature of the reaction may vary considerably, for example, from about 20 Celsius to the boiling point of the substituted benzene compound.
Preferably, the reaction temperature is maintained at 60 to 1600 Celsius. At lower temperatures, increased formation of undesirable substituted diphenyl sulfides is likely to occur. The process is preferably carried out at atmospheric pressure, although subatmospheric and superatmospheric conditions may be employed, if desired, with appropriate adjustments in the upper temperature limit.
Upon completion of the reaction, the reaction vessel is cooled to room temperature and the contents filtered. The filtrate, consiting of substituted benzene compound and unwanted reaction by-products and impurities is removed and the remaining solids, a substituted thianthrene aluminum chloride complex, are slurried in the inert organic liquid, such a monochlorotoluene or benzene. A Lewis base, such as anhydrous ammonia, is passed, as by sparging through the slurry, preferably at a temperature of between 25"C and 65"C to break the insoluble complex and separate the substituted thianthrene in the soluble phase. The amount of Lewis base employed may vary considerably. Essentially complete separation, under the conditions shown may generally be accomplished with the addition of between 0.3 to and 0.5 parts by weight of ammonia per part of crude complex. Aluminum chloride and any residual sulfur form insoluble complexes which are then filtered from the solution. The product substituted thianthrene can then be recovered in high yields by evaporation and crystallization of the liquor.
The most preferred substituted thianthrenes which may be prepared in accordance with this invention are the di- and tetra-substituted thianthrenes wherein the substituents are selected from methyl and chlorine. Such compounds are prepared in the manner described from an appropriately substituted benzene compound having at least two adjacent ring positions unsubsituted. Most preferred are mono and di-substituted benzene compounds wherein the substituents are independently selected from methyl and chlorine. Thus, the preferred substituted benzene compound starting materials include for example, toluene, orthochlorotoluene, parachlorotoluene, metachlorotoluene, paraxylene orthoxylene, metaxylene. The particular substituted thianthrene prepared will depend on the position of the substituents on the benzene ring, and in some instances may be a mixture of substituted thianthrenes. Thus, for example, when paraxylene is employed as the starting material, the product will be 1,4,6,9-tetramethylthianthrene. When the starting material is metaxylene, the product will be a mixture of the 1,3,6,8- and 1,3,7,9-isomers of tetramethylthianthrene.
Various Lewis bases may be employed in recovering the substituted thianthrene from the complex. Typical Lewis bases include for example, ammonia, pyridine and diethylamine.
Based on efficiency, cost and availability, the preferred Lewis base is ammonia. The organic solvent in which the thianthrene compound-aluminum chloride complex is slurried is selected on the basis of three primary considerations. First, the solvent must be-one in which the substituted thianthrene is soluble. Second, the solvent must be substantially inert to ammonia or other Lewis base employed. In addition, the solvent must be one in which the complex is substantially insoluble. Solvents suitable for this purpose include for example, benzene, monochlorobenzene, toluene, monochlorotoluene, tetrahydrofuran, carbon tetrachloride, chloroform, acetylene, tetrachloride, perchloroethylene, trichloroethylene and xylene, as mixtures thereof, and other organic solvents that meet the considerations set forth above. Optionally, all or a part of the solvent employed may be an excess of the substituted benzene compound reactant. Thus, for example, in the preparation of dimethyldichlorothianthrene from sulfur monochloride and orthochlorotoluene in the presence of the orthochlorotoluene may be used and will serve as a solvent for the dimethyldichlorothianthrene when the latter is separated from the complex. Additional amounts of the same or other suitable solvent may be added.
The following Example will serve to further illustrate the invention and the manner in which it may be practised. In the Example, unless otherwise stated, all parts and percentages are by weight.
Example
A mixture of 126.5 parts of orthochlorotoluene and 13.35 parts of aluminum chloride was stirred and heated to about 40"C. Stirring was continued and the temperature maintained while 22.5 parts of sulfur monochloride was added slowly to the mixture over a period of about one half hour. After completion of the sulfur monochloride addition, the temperature of the reaction mixture was maintained at about 40"C. Ammonia was then bubbled slowly into the reaction mixture until the reaction mixture changed in color from a dark green-blue to a yellow. At this point 159 parts of chloroform was added and the solution of ammonia was continued until the reaction mixture was found to be alkaline to litmus paper. The mixture was filtered and washed with chloroform. Gas chromatographic analysis of the filtrate indicated a 56.6 percent yield of thianthrene product, based on sulfur monochloride, containing approximately 33 percent dimethylthianthrene, 23 percent dimethylmonochlorothianthrene, and 44 percent dimethyldichlorothianthrene.
WHAT WE CLAIM IS:
1. A process for separating a substututed thianthrene of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or fluorine, subject to the proviso that not all X's on each benzene ring are hydrogen, from a complex thereof with aluminum chloride, which process comprising mixing the complex with an organic liquid which is a solvent for the substituted thianthrene but not for the complex or for aluminum chloride to form a slurry of the complex, and treating the slurry with a Lewis base to which the organic liquid is inert to free the substituted thianthrene from the complex and to allow the substituted thianthrene to dissolve in the organic liquid.
2. A process according to claim 1 wherein the Lewis base is ammonia.
3. A process according to claim 1 wherein the Lewis base is diethylamine.
4. A process according to claim 1 wherein the Lewis base is pyridine.
5. A process according to any one of the preceding claims wherein the substituted thianthrene is a dimethyldichlorothianthrene.
6. A process according to any one of the preceding claims wherein the organic liquid is a monochlorotoluene.
7. A process according to any of claims 1 to 5 wherein the organic liquid is chloroform.
8. A process according to any one of the preceding claims wherein the complex has
been prepared by adding, in the presence of aluminum chloride, sulphur monochloride to a
stoichiometric excess of a substituted benzene compound of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (12)
1. A process for separating a substututed thianthrene of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or fluorine, subject to the proviso that not all X's on each benzene ring are hydrogen, from a complex thereof with aluminum chloride, which process comprising mixing the complex with an organic liquid which is a solvent for the substituted thianthrene but not for the complex or for aluminum chloride to form a slurry of the complex, and treating the slurry with a Lewis base to which the organic liquid is inert to free the substituted thianthrene from the complex and to allow the substituted thianthrene to dissolve in the organic liquid.
2. A process according to claim 1 wherein the Lewis base is ammonia.
3. A process according to claim 1 wherein the Lewis base is diethylamine.
4. A process according to claim 1 wherein the Lewis base is pyridine.
5. A process according to any one of the preceding claims wherein the substituted thianthrene is a dimethyldichlorothianthrene.
6. A process according to any one of the preceding claims wherein the organic liquid is a monochlorotoluene.
7. A process according to any of claims 1 to 5 wherein the organic liquid is chloroform.
8. A process according to any one of the preceding claims wherein the complex has
been prepared by adding, in the presence of aluminum chloride, sulphur monochloride to a
stoichiometric excess of a substituted benzene compound of the formula
wherein each X independently represents hydrogen, methyl, ethyl, chlorine, bromine or
fluorine, subject to the proviso that not all X's are hydrogen.
9. A process according to claim 8 wherein the substituted benzene compound is orthochlorotoluene.
10. A process according to claim 1 substantially as described with reference to the
Examples.
11. A process according to any one of the preceding claims wherein a solution of a substituted thianthrene in an organic liquid is separated from the solids present and the substituted thianthrene is recovered from the solution in known manner.
12. A substituted thianthrene when prepared by a process as claimed in claim 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/737,320 US4091031A (en) | 1974-11-05 | 1976-11-01 | Process for the manufacture of substituted thianthrene based products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1575853A true GB1575853A (en) | 1980-10-01 |
Family
ID=24963442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3531077A Expired GB1575853A (en) | 1976-11-01 | 1977-08-23 | Process for the manufacture and separation of substituted thianthrenes |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5356673A (en) |
| BE (1) | BE860090A (en) |
| BR (1) | BR7705620A (en) |
| CA (1) | CA1064947A (en) |
| DE (1) | DE2739217A1 (en) |
| FR (1) | FR2369277A1 (en) |
| GB (1) | GB1575853A (en) |
| IT (1) | IT1087969B (en) |
| NL (1) | NL7710640A (en) |
-
1977
- 1977-08-16 JP JP9861977A patent/JPS5356673A/en active Pending
- 1977-08-23 GB GB3531077A patent/GB1575853A/en not_active Expired
- 1977-08-23 BR BR7705620A patent/BR7705620A/en unknown
- 1977-08-31 DE DE19772739217 patent/DE2739217A1/en not_active Withdrawn
- 1977-09-29 NL NL7710640A patent/NL7710640A/en not_active Application Discontinuation
- 1977-10-25 BE BE182042A patent/BE860090A/en not_active IP Right Cessation
- 1977-10-26 IT IT2900177A patent/IT1087969B/en active
- 1977-10-26 CA CA289,590A patent/CA1064947A/en not_active Expired
- 1977-10-27 FR FR7732457A patent/FR2369277A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7710640A (en) | 1978-05-03 |
| FR2369277B1 (en) | 1982-09-10 |
| DE2739217A1 (en) | 1978-05-11 |
| BR7705620A (en) | 1978-06-06 |
| CA1064947A (en) | 1979-10-23 |
| BE860090A (en) | 1978-04-25 |
| JPS5356673A (en) | 1978-05-23 |
| FR2369277A1 (en) | 1978-05-26 |
| IT1087969B (en) | 1985-06-04 |
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