CA1270853A - Process for preparing (hydrocarbylthio) aromatic amines - Google Patents
Process for preparing (hydrocarbylthio) aromatic aminesInfo
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- CA1270853A CA1270853A CA000531365A CA531365A CA1270853A CA 1270853 A CA1270853 A CA 1270853A CA 000531365 A CA000531365 A CA 000531365A CA 531365 A CA531365 A CA 531365A CA 1270853 A CA1270853 A CA 1270853A
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- Prior art keywords
- aromatic
- iodide
- metal halide
- hydrocarbylthio
- hydrocarbyl
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Abstract
ABSTRACT
PROCESS FOR PREPARING (HYDROCARBYLTHIO)AROMATIC AMINES
(Hydrocarbylthio)aromatic polyamines are prepared by reacting an aromatic polyamine, such as a diamino-benzene, with a hydrocarbyl disulfide, such as an alkyl disulfide, in the presence of an iodide or bromide of a metal other than an alkali metal as a catalyst.
PROCESS FOR PREPARING (HYDROCARBYLTHIO)AROMATIC AMINES
(Hydrocarbylthio)aromatic polyamines are prepared by reacting an aromatic polyamine, such as a diamino-benzene, with a hydrocarbyl disulfide, such as an alkyl disulfide, in the presence of an iodide or bromide of a metal other than an alkali metal as a catalyst.
Description
70~53 Case 5526 PROCESS FOR PREPARING tHYDROCARBYLTHIO~AROMATIC AMINE5 This invention relates to (hydrocarbylthio)aromatic polyamines and more particularly to a process for prepar-ing them.
As disclosed in u. s. Patent 4,594,453 (Ranken et al . ), it is known that various (hydrocarbylthio)aromatic amines are useful as intermediates in the preparation of polyurethanes~ and they can be prepared by reacting an __ aromatic amine with a hydrocarbyl disulfide in the 10 presence of a catalytic amount of a Lewis acid. The preferred catalysts of Ranken et al. are metal halides, such as aluminum chloride, boron trifluoride, boron trichloride, ferric chloride, and zinc chloride.
- In the case of the diamines, it has been found that 15 the preferred catalysts identified by Ranken et al. have the disadvantages of effecting the desired hydrocarbyl-thiations at too slow a rate to be completely satisfactory and of sometimes providing too low a yield of product.
An object of this invention is to provide a novel 20 process for preparing (hydrocarbylthio)aromatic diamines.
Another object is to provide such a process wherein the products are prepared by the hydrocarbylthiation of 12 7~
aromatic polyamines in the presence of metal halide catalysts.
A further object is to provide such a process wherein the reaction rates and/or product yields are 5 improved.
These and other objects are attained by reacting an aromatic polyamine with a hydrocarbyl disulfide in the presence of a catalytic amount of an iodide or bromide of a metal other than an alkal i metal.
Aromatic polyamines utilizable in the practice of _ the invention are compounds ha~ing at least two amino groups attached to a carbocyclic or heterocyclic ring of an aromatic compound containing one or more simple and/or fused rings, such as benzene, naphthalene, anthracene, 15 pyrrole, pyridine and indole. The compounds may bear no - substituents other than the required amino groups, or they may bear substituents inert to the reaction conditions, such as chloro, fluoro, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, alkaryl, or aralkyl groups on any 20 positions other than those to be substituted by hydro-carbylthio groups. In the case of coupled aromatic rings, the rings may be directly attached to one another or may.
be coupled through a bridge such as an oxygen, sulfur, sulfoxide, sulfone, alkyl, or other hydrocarbon link.
25 Useful aromatic polyamines include, for example, 1,5-diaminonaphthalene, 2,6-diaminopyridine, 1,2-diamino-benzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1~70~5~3
As disclosed in u. s. Patent 4,594,453 (Ranken et al . ), it is known that various (hydrocarbylthio)aromatic amines are useful as intermediates in the preparation of polyurethanes~ and they can be prepared by reacting an __ aromatic amine with a hydrocarbyl disulfide in the 10 presence of a catalytic amount of a Lewis acid. The preferred catalysts of Ranken et al. are metal halides, such as aluminum chloride, boron trifluoride, boron trichloride, ferric chloride, and zinc chloride.
- In the case of the diamines, it has been found that 15 the preferred catalysts identified by Ranken et al. have the disadvantages of effecting the desired hydrocarbyl-thiations at too slow a rate to be completely satisfactory and of sometimes providing too low a yield of product.
An object of this invention is to provide a novel 20 process for preparing (hydrocarbylthio)aromatic diamines.
Another object is to provide such a process wherein the products are prepared by the hydrocarbylthiation of 12 7~
aromatic polyamines in the presence of metal halide catalysts.
A further object is to provide such a process wherein the reaction rates and/or product yields are 5 improved.
These and other objects are attained by reacting an aromatic polyamine with a hydrocarbyl disulfide in the presence of a catalytic amount of an iodide or bromide of a metal other than an alkal i metal.
Aromatic polyamines utilizable in the practice of _ the invention are compounds ha~ing at least two amino groups attached to a carbocyclic or heterocyclic ring of an aromatic compound containing one or more simple and/or fused rings, such as benzene, naphthalene, anthracene, 15 pyrrole, pyridine and indole. The compounds may bear no - substituents other than the required amino groups, or they may bear substituents inert to the reaction conditions, such as chloro, fluoro, alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, alkaryl, or aralkyl groups on any 20 positions other than those to be substituted by hydro-carbylthio groups. In the case of coupled aromatic rings, the rings may be directly attached to one another or may.
be coupled through a bridge such as an oxygen, sulfur, sulfoxide, sulfone, alkyl, or other hydrocarbon link.
25 Useful aromatic polyamines include, for example, 1,5-diaminonaphthalene, 2,6-diaminopyridine, 1,2-diamino-benzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 1~70~5~3
2,4-diaminotoluene, 2,6-diaminotoluene and 2,6-diamino-1--ethylbenzene.
Hydrocarbyl disulfides which may be reacted with the aromatic polyamines include saturated and unsaturated 5 aliphatic, cycloaliphatic, and aromatic disulfides in which the hydrocarbyl groups optionally bear inert, such as chloro, substituents. Exemplary of such compounds are methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, 2-chloropentyl, cyclopentyl, cyclohexyl, phenyl, benzyl, 10 p-tolyl, and p-chlorophenyl disulfides. This component Of _ the reaction mixture is generally employed in at least the stoichiometric amount required ~O yield the desired (hydrocarbylthio)aromatic a~ine; that i5, at least an equimolar amount being used when a mono(hydrocarbylthio)-15 aromatic amine is desired, and at least two molar -- equivalents being utilized when a di(hydrocarbylthio)-aromatic amine is desired.
The reaction of the aromatic polyamine with the hydrocarbyl disulfide is generally conducted at a tempera-20 ture in the range of 20-300C., preferably 100-200C., and at a pressure of atmospheric up to 1000 psi; and/ as men-tioned above, it is conducted in the presence of a cata-lytic amount of a non-alkali metal iodide or bromide.
Metal iodides and bromides that can be used in the 25 practice of the invention can be any of the known Lewis acid catalysts which are iodides or bromides of metals ~7(~h~3 other than alkali metals, such as the ferrous, ferric, cuprous, cupric, zinc, cadmium, lead, cobaltous, mercu-rous, and mercuric iodides and bromides. The preferred catalysts, however, are the iodides, especially cuprous, ferrous, cobaltous, cadmium, and zinc iodides. The catalyst is employed in catalytic amounts, generally in a catalyst/aromatic amine mol ratio of 0.01-0.5/1, preferably 0.01-0.2/1.
In conducting the process of the invention, it is frequently preferred to (1~ heat a mixture of the catalyst --_ and aromatic polyamine at a suitable temperature, usually a temperature higher than the boiling point of the disul-fide to be added, usually 100-150C., until all of the catalyst has reacted and then (2~ maintain the reaction mixture at reflux temperature after the disulfide has been - added to effect a hydrocarbylthiation process while removing evolved hydrocarbyl thiol by-product from the reaction vessel. It is also satisfactory to conduct the process by simply mixing the catalyst and reactants together and heating them to the reflux temperature. An inert solvent may be employed if desired~ The metal iodide or bromide may be used in conjunction with another catalyst or a promoter, such as boron trifluoride etherate.
The process of the invention, like the process of Ranken et al., results in the formation of (hydrocarbyl-thio)aromatic amines which are useful as intermediates in ~7~
the preparation of polyurethanes. It is particularly advantageous in that it is characterized by higher reac-tion rates and/or higher yields than are obtained when the metal chlorides of Ranken et al. are used.
The following examples are given to illustrate the invention and are not intended as a limitation thereof.
COMPARATIVE EXAMPLE A
One molar proportion of commercial toluenediamine (C-TDA) -- a material containing 80% 2,4-diaminotoluene and 20~ 2,6-diaminotoluene -- was heated with 0.065 molar proportion of aluminum chloride at 150C. for one hour.
Methyl disulfide was then added in sufficient excess to maintain the reaction temperature at 135C., and the reaction was conducted for 39 hours to achieve 100% con-version of the c-TDA. Analysis of the product showed it to contain 16 mol% mono(methylthio) derivatives of c-TDA
(MMTDA), 78 mol% di(methylthio) derivatives of c-TDA
(DMTDA), and 6 mol% by-products.
EXAMPLE I
Each of seventeen reactions was conducted essen-tially as described in comparative Example A except ~or substituting 0.05 molar proportion of another catalyst for the 0.065 molar proportion of aluminum chloride. The catalysts employed, the reaction times required, the conversions obtained, and the percentages of MMTDA and DMTDA in the final product are shown below.
1~7(~;353 MetalTime conversion % Yield Halide(Hrs.) (%~ MMTDADMTDA
FeBr3 22 90 56 43 FeBr2 22 98 39 61 FeI2 5 99 26 73 PbI2 7 94 50 50 Cu2I2 10 100 5 94 Cu2Br220 85 70 30 HgI2 10 loO 11 87 . Hg2I2 10 100 16 81 CdI2 5 100 27 72 ZnBr2 14 87 78 23 ZnI2 20 98 29 68 - AgI 17 61 92 8 CoI2 3.5 100 21 77 lOo 16 80 - Comparative Example A was essentially repeated except that 0.045 molar proportion of zinc bromide was substituted for the aluminum chloride and the reaction time was only 21 hours. The reaction resulted in 95%
25 conversion, and analysis showed the product to contain 46 mol% MMTDA and 54 mol% DMTDA.
EXAMPLE III
Comparative Example A was essentially repeated except that 0.044 molar proportion of zinc iodide was sub-stituted for the aluminum chloride and the reaction time was only 19 hours. The reaction resulted in 98% conver-sion, and analysis showed the product to contain 30 mol%
MMTDA and 68 mol% DMTDA.
EXAMPLE IV
- Compaxative Example A was essentially repeated except that 0.02 molar proportion of zinc iodide and 0.033 ~ molar proportion of boron trifluoride etherate were sub-stituted for the aluminum chloride and the reaction time was only 20.5 hours. The reaction resulted in 100% con-version, and analysis showed the product to contain 12 mol% MMTDA and 86 mol% DMTDA.
COMPARATIVE EXAMPLE B
Comparative Example A was essentially repeated except that 0.05 molar proportion of boron trifluoride etherate was substituted for the aluminum chloride and the reaction was continued for only 7.5 hours, at,which time it was terminated because of the substantial absence of any reaction.
It is obvious that many variations may be made in the products and processes set forth above without departing from the spirit and scope of this invention.
Hydrocarbyl disulfides which may be reacted with the aromatic polyamines include saturated and unsaturated 5 aliphatic, cycloaliphatic, and aromatic disulfides in which the hydrocarbyl groups optionally bear inert, such as chloro, substituents. Exemplary of such compounds are methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, 2-chloropentyl, cyclopentyl, cyclohexyl, phenyl, benzyl, 10 p-tolyl, and p-chlorophenyl disulfides. This component Of _ the reaction mixture is generally employed in at least the stoichiometric amount required ~O yield the desired (hydrocarbylthio)aromatic a~ine; that i5, at least an equimolar amount being used when a mono(hydrocarbylthio)-15 aromatic amine is desired, and at least two molar -- equivalents being utilized when a di(hydrocarbylthio)-aromatic amine is desired.
The reaction of the aromatic polyamine with the hydrocarbyl disulfide is generally conducted at a tempera-20 ture in the range of 20-300C., preferably 100-200C., and at a pressure of atmospheric up to 1000 psi; and/ as men-tioned above, it is conducted in the presence of a cata-lytic amount of a non-alkali metal iodide or bromide.
Metal iodides and bromides that can be used in the 25 practice of the invention can be any of the known Lewis acid catalysts which are iodides or bromides of metals ~7(~h~3 other than alkali metals, such as the ferrous, ferric, cuprous, cupric, zinc, cadmium, lead, cobaltous, mercu-rous, and mercuric iodides and bromides. The preferred catalysts, however, are the iodides, especially cuprous, ferrous, cobaltous, cadmium, and zinc iodides. The catalyst is employed in catalytic amounts, generally in a catalyst/aromatic amine mol ratio of 0.01-0.5/1, preferably 0.01-0.2/1.
In conducting the process of the invention, it is frequently preferred to (1~ heat a mixture of the catalyst --_ and aromatic polyamine at a suitable temperature, usually a temperature higher than the boiling point of the disul-fide to be added, usually 100-150C., until all of the catalyst has reacted and then (2~ maintain the reaction mixture at reflux temperature after the disulfide has been - added to effect a hydrocarbylthiation process while removing evolved hydrocarbyl thiol by-product from the reaction vessel. It is also satisfactory to conduct the process by simply mixing the catalyst and reactants together and heating them to the reflux temperature. An inert solvent may be employed if desired~ The metal iodide or bromide may be used in conjunction with another catalyst or a promoter, such as boron trifluoride etherate.
The process of the invention, like the process of Ranken et al., results in the formation of (hydrocarbyl-thio)aromatic amines which are useful as intermediates in ~7~
the preparation of polyurethanes. It is particularly advantageous in that it is characterized by higher reac-tion rates and/or higher yields than are obtained when the metal chlorides of Ranken et al. are used.
The following examples are given to illustrate the invention and are not intended as a limitation thereof.
COMPARATIVE EXAMPLE A
One molar proportion of commercial toluenediamine (C-TDA) -- a material containing 80% 2,4-diaminotoluene and 20~ 2,6-diaminotoluene -- was heated with 0.065 molar proportion of aluminum chloride at 150C. for one hour.
Methyl disulfide was then added in sufficient excess to maintain the reaction temperature at 135C., and the reaction was conducted for 39 hours to achieve 100% con-version of the c-TDA. Analysis of the product showed it to contain 16 mol% mono(methylthio) derivatives of c-TDA
(MMTDA), 78 mol% di(methylthio) derivatives of c-TDA
(DMTDA), and 6 mol% by-products.
EXAMPLE I
Each of seventeen reactions was conducted essen-tially as described in comparative Example A except ~or substituting 0.05 molar proportion of another catalyst for the 0.065 molar proportion of aluminum chloride. The catalysts employed, the reaction times required, the conversions obtained, and the percentages of MMTDA and DMTDA in the final product are shown below.
1~7(~;353 MetalTime conversion % Yield Halide(Hrs.) (%~ MMTDADMTDA
FeBr3 22 90 56 43 FeBr2 22 98 39 61 FeI2 5 99 26 73 PbI2 7 94 50 50 Cu2I2 10 100 5 94 Cu2Br220 85 70 30 HgI2 10 loO 11 87 . Hg2I2 10 100 16 81 CdI2 5 100 27 72 ZnBr2 14 87 78 23 ZnI2 20 98 29 68 - AgI 17 61 92 8 CoI2 3.5 100 21 77 lOo 16 80 - Comparative Example A was essentially repeated except that 0.045 molar proportion of zinc bromide was substituted for the aluminum chloride and the reaction time was only 21 hours. The reaction resulted in 95%
25 conversion, and analysis showed the product to contain 46 mol% MMTDA and 54 mol% DMTDA.
EXAMPLE III
Comparative Example A was essentially repeated except that 0.044 molar proportion of zinc iodide was sub-stituted for the aluminum chloride and the reaction time was only 19 hours. The reaction resulted in 98% conver-sion, and analysis showed the product to contain 30 mol%
MMTDA and 68 mol% DMTDA.
EXAMPLE IV
- Compaxative Example A was essentially repeated except that 0.02 molar proportion of zinc iodide and 0.033 ~ molar proportion of boron trifluoride etherate were sub-stituted for the aluminum chloride and the reaction time was only 20.5 hours. The reaction resulted in 100% con-version, and analysis showed the product to contain 12 mol% MMTDA and 86 mol% DMTDA.
COMPARATIVE EXAMPLE B
Comparative Example A was essentially repeated except that 0.05 molar proportion of boron trifluoride etherate was substituted for the aluminum chloride and the reaction was continued for only 7.5 hours, at,which time it was terminated because of the substantial absence of any reaction.
It is obvious that many variations may be made in the products and processes set forth above without departing from the spirit and scope of this invention.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for reacting an aromatic polyamine With a hydrocarbyl disulfide in the presence of a catalytic amount of a metal halide to form a (hydrocarbyl-thio)aromatic amine, characterized by the metal halide being an iodide or bromide of a metal other than an alkali metal.
2. A process as claimed in claim 1 in Which the aromatic polyamine is a diaminobenzene.
3. The process as claimed in claim 2 in which the diaminobenzene is a diaminotoluene.
4. A process as claimed in claim 1 in which the hydrocarbyl disulfide is methyl disulfide.
5. A process as claimed in claim 1 in which the metal halide is zinc iodide.
6. A process as claimed in claim 1 in which the metal halide is cuprous iodide.
7. A process as claimed in claim 1 in which the metal halide is ferrous iodide.
8. A process as claimed in claim l in which the metal halide is cadmium iodide.
9. A process as claimed in claim 1 in which the metal halide is cobaltous iodide.
10. A process as claimed in claim 1 in which the aromatic polyamine is a mixture containing 2,4-diamino-toluene and 2,6-diaminotoluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000531365A CA1270853A (en) | 1987-03-06 | 1987-03-06 | Process for preparing (hydrocarbylthio) aromatic amines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000531365A CA1270853A (en) | 1987-03-06 | 1987-03-06 | Process for preparing (hydrocarbylthio) aromatic amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1270853A true CA1270853A (en) | 1990-06-26 |
Family
ID=4135113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000531365A Expired CA1270853A (en) | 1987-03-06 | 1987-03-06 | Process for preparing (hydrocarbylthio) aromatic amines |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1270853A (en) |
-
1987
- 1987-03-06 CA CA000531365A patent/CA1270853A/en not_active Expired
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