GB2106097A - Process for the preparation of cyanoanilines - Google Patents
Process for the preparation of cyanoanilines Download PDFInfo
- Publication number
- GB2106097A GB2106097A GB08218140A GB8218140A GB2106097A GB 2106097 A GB2106097 A GB 2106097A GB 08218140 A GB08218140 A GB 08218140A GB 8218140 A GB8218140 A GB 8218140A GB 2106097 A GB2106097 A GB 2106097A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ester
- phosphonate
- sulphonate
- acid
- sulphonic
- 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.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 11
- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical class N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 title description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims abstract description 4
- WCFLBCQUEZKJJD-UHFFFAOYSA-N 2-aminofuran-3-carbonitrile Chemical compound NC=1OC=CC=1C#N WCFLBCQUEZKJJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- -1 sulphonate ester Chemical class 0.000 claims description 8
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000013067 intermediate product Substances 0.000 claims description 3
- 150000001448 anilines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- IUJPJWUMEHQHRX-UHFFFAOYSA-N 2-amino-3-cyanobenzenesulfonic acid Chemical compound C(#N)C1=C(N)C(=CC=C1)S(=O)(=O)O IUJPJWUMEHQHRX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ACHDPRAJHGRGDC-UHFFFAOYSA-N 2-amino-4,5-dimethylfuran-3-carbonitrile Chemical compound CC=1OC(N)=C(C#N)C=1C ACHDPRAJHGRGDC-UHFFFAOYSA-N 0.000 description 1
- JXPDNDHCMMOJPC-UHFFFAOYSA-N 2-hydroxybutanedinitrile Chemical compound N#CC(O)CC#N JXPDNDHCMMOJPC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3834—Aromatic acids (P-C aromatic linkage)
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
2-cyano, 6 sulphonic acid or sulphonic ester or 6-phosphonic acid or phosphonic ester derivatives of analine are prepared by reaction of a vinyl sulphonate or vinyl phosphonate and an (optionally substituted) 2-amino-3-cyanofuran followed by dehydration of the product formed. The compounds are useful as intermediates in the preparation of diazo components for the manufacture of anionic dyestuffs.
Description
SPECIFICATION
Process for the preparation of cyanoanilines
This invention relates to a process for the preparation of cyanoanilines, and in particular to a process for the preparation of cyanoanilines containing a sulphonic acid or sulphonic ester group or a phosphonic acid or phosphonic ester group.
According to the present invention there is provided a process for the preparation of 2cyano, 6-sulphonic acid or sulphonic ester or 6-phosphonic acid or phosphonic ester derivatives of anilines which comprises reacting a 2amino-3-cyanofuran of formula:
with a vinyl sulphonate ester or a vinyl phosphonate or phosphonate ester of formula:
CH2 ----- CHX (II) wherein R, and R2 may be hydrogen or a hydrocarbyl group and X is a sulphonate or a sulphonate ester group or is a phosphonate or phosphonate ester group, and dehydrating the intermediate product formed.
R, and R2, which may be the same or different, may be hydrogen or a hydrocarbyl group for example an (optionally substituted) alkyl group, an (optionally substituted) aryl group, a carboxylic acid group, a carboxylic ester group or a cyano group. The furan starting material may be readily prepared by known methods, for example by the reaction of malonitrile with the appropriately substituted alpha hydroxy ketone.
When the group X is sulphonic or phosphonic ester, it is suitable an alkyl or aryl ester, for example an ester (or bis-ester) of an alkyl group containing from 1 to 20 carbon atoms.
Whilst the scope of the present invention is not to be taken as being limited by any particular theory, the initial product of the reaction is believed to be a hydroxy compound of formula:
which is dehydrated to give the desired product. The intermediate product may be isolated if desired, by the dehydration conventiently takes place in situ.
The reaction may take place in a solvent or in the absence of a solvent. Suitable solvents are oxygen-containing solvents, including ethers, for example dimethoxyethane or dioxan.
The optimum reaction temperature depends upon the reactants and the conditions employed, but will in general be in the range from 60"C to 1 50 C. For example, in the reaction of a furan with a vinyl phosphonate in the absence of a solvent, a reaction temperature of from 85"C to 1 50 C, for example from 11 0,C to 1 50 C is conveniently employed. A reaction which takes place in a solvent such as dimethoxyethane conveniently takes place close to the boiling point of the solvent, i.e. 70"C to 80"C. A reaction time of from + to 24 hours may be required.
Dehydration of the intermediate compound may take place in the presence of water, or preferably in an acid, for example a dilute mineral acid and/or glacial acetic acid. Thus the reaction mixture may be added directly to the acid, whereupon the desired product precipitates and may be recovered. Alternatively, the reaction mixture may be added to water and dehydration of the precipitate completed by addition to dilute acid.
It is not essential to employ a catalyst for the reaction, but a catalyst, for example a
Lewis acid, may be used if desired.
The proportions of the reactants are not critical and may be essentially stoichiometric.
A slight excess of vinyl sulphonate or phosphonate over the furan may assist the subsequent isolation of the desired product, for example from 1.05 to 5 moles of vinyl sulphonate or phosphonate per mole of furan may be used.
The reaction suitably takes place under atmospheric conditions of pressure.
It is an advantage of the process of the present invention that the reaction is substantially specific for the formation of the 2-cyano, 6-sulphonic acid or ester or 6-phosphonic acid or ester derivative of aniline.
The compounds of the present invention are useful as intermediates in the formation of diazo components, for example in the manufacture of anionic dyestuffs.
The invention is illustrated by the following Examplres in which all parts and percentages are by weight unless otherwise stated.
Example 1 2-amino-3-cyano-4,5-dimethylfuran (2.72 g) was added in portions over a period of 10 hours to vinyl phosphonic acid, bis-(beta-chloroethyl)ester(CH2 = CH-PO(OCH2CH2C1)2), which was maintained at a temperature of 1 1 0 C. The resultant brown oil was stirred with glacial acetic acid (25 ml) and dilute sulphuric acid (2 ml) for 1 hour. The product was extracted into chloroform, and the organic layer was washed with water and dried over magnesium sulphate. The solvent was removed to give the bis(beta chloroethyl) ester of 2-cyano-aniline-6-phosphonic acid (melting point 82"C) in 65% yield.
Example 2.
The product of Example 1 was stirred with 32% sodium hydroxide solution for 30 minutes, and then acidified. The solid product was filtered to give 2-cyanoaniline-6-phosphonic acid (melting point 210"C ) in 70% yield.
Example 3
2-Amino-3-cyano-4, 5-diemethylfuran (6.8 g) was added to a refluxing solution of methylvinylsulphonate (6.1 g) in 1,2-dimethoxyethane over a period of 5 hours. After a further hour, the solvent was removed and the residue added to glacial acetic acid (50 ml) containing sulphuric acid (4 ml). The mixture was stirred for 30 minutes and the solid product filtered and dried. The product was the methyl ester of 2-cyanoaniline-6-sulphonic acid (melting point 148-149"C), which was obtained in 75% yield.
Example 4
The product of Example 3 was suspended in water and treated with hot sodium hydroxide for 5 minutes. After acidification, the solid product was filtered to give a yield of 60%.
The product was 2-cyanoaniline-6-sulphonic acid (melting point: decomposes above 1 28 C).
Claims (4)
1. A process for the preparation of 2cyano, 6-sulphonic acid or sulphonic ester or 6-phosphonic acid or phosphonic ester derivatives of anilines which comprises reacting a 2amino-3-cyanofuran of formula:
with a vinyl sulphonate or sulphonate ester or a vinyl phosphonate or phosphonate ester of formula:
CH2- CHX (II) wherein R, and R2 may be hydrogen or a hydrocarbyl group and X is a sulphonate or a sulphonate ester group or is a phosphonate or a phosphonate ester group, and dehydrating the intermediate product formed.
2. A process according to claim 1 wherein the group X is an alkyl or aryl sulphonic or phosphonic ester or bis ester containing from 1 to 20 carbon atoms.
3. A process according to claim 1 or 2 wherein the reaction temperature is from 60"C to 1 50 C.
4. A process according to any of the preceding claims wherein there is used from 1.05 to 5 moles of vinyl sulphonate or phosphonate per mole of furan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08218140A GB2106097A (en) | 1981-09-21 | 1982-06-23 | Process for the preparation of cyanoanilines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8128517 | 1981-09-21 | ||
| GB08218140A GB2106097A (en) | 1981-09-21 | 1982-06-23 | Process for the preparation of cyanoanilines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2106097A true GB2106097A (en) | 1983-04-07 |
Family
ID=26280766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08218140A Withdrawn GB2106097A (en) | 1981-09-21 | 1982-06-23 | Process for the preparation of cyanoanilines |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2106097A (en) |
-
1982
- 1982-06-23 GB GB08218140A patent/GB2106097A/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |