US2985688A - Production of substituted nitrophenols - Google Patents
Production of substituted nitrophenols Download PDFInfo
- Publication number
- US2985688A US2985688A US454818A US45481854A US2985688A US 2985688 A US2985688 A US 2985688A US 454818 A US454818 A US 454818A US 45481854 A US45481854 A US 45481854A US 2985688 A US2985688 A US 2985688A
- Authority
- US
- United States
- Prior art keywords
- substituted
- nitro
- nitrophenol
- chlorophenol
- production
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 title claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006396 nitration reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 150000002989 phenols Chemical group 0.000 claims description 13
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 13
- 230000000802 nitrating effect Effects 0.000 claims description 10
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 7
- -1 METHYL GROUPS Chemical group 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 4
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical class OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 description 9
- DKTRZBWXGOPYIX-UHFFFAOYSA-N 3-chloro-4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(Cl)=C1 DKTRZBWXGOPYIX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- JUIKCULGDIZNDI-UHFFFAOYSA-N 4-chloro-3-nitrophenol Chemical compound OC1=CC=C(Cl)C([N+]([O-])=O)=C1 JUIKCULGDIZNDI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- JXVQRZMAWKEHFN-UHFFFAOYSA-N tris(3-chlorophenyl) phosphate Chemical compound ClC1=CC=CC(OP(=O)(OC=2C=C(Cl)C=CC=2)OC=2C=C(Cl)C=CC=2)=C1 JXVQRZMAWKEHFN-UHFFFAOYSA-N 0.000 description 4
- AQJFATAFTQCRGC-UHFFFAOYSA-N 2-Chloro-4-methylphenol Chemical compound CC1=CC=C(O)C(Cl)=C1 AQJFATAFTQCRGC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- HFJRPDALZHECPK-UHFFFAOYSA-N 2-chloro-4-methyl-5-nitrophenol Chemical compound CC1=CC(Cl)=C(O)C=C1[N+]([O-])=O HFJRPDALZHECPK-UHFFFAOYSA-N 0.000 description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 2
- NWSIFTLPLKCTSX-UHFFFAOYSA-N 4-chloro-2-nitrophenol Chemical compound OC1=CC=C(Cl)C=C1[N+]([O-])=O NWSIFTLPLKCTSX-UHFFFAOYSA-N 0.000 description 2
- MZDBQSFPAMTTIS-UHFFFAOYSA-N 5-chloro-2-nitrophenol Chemical compound OC1=CC(Cl)=CC=C1[N+]([O-])=O MZDBQSFPAMTTIS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DFQHFXCKNSCDFW-UHFFFAOYSA-N tris(4-chlorophenyl) phosphate Chemical compound C1=CC(Cl)=CC=C1OP(=O)(OC=1C=CC(Cl)=CC=1)OC1=CC=C(Cl)C=C1 DFQHFXCKNSCDFW-UHFFFAOYSA-N 0.000 description 2
- GZELFOWMRSGSTI-UHFFFAOYSA-N (3-methylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(OP(O)(O)=O)=C1 GZELFOWMRSGSTI-UHFFFAOYSA-N 0.000 description 1
- BBAMTDMNXVSCRU-UHFFFAOYSA-N (4-chlorophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=C(Cl)C=C1 BBAMTDMNXVSCRU-UHFFFAOYSA-N 0.000 description 1
- JNUCNIFVQZYOCP-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C=C1 JNUCNIFVQZYOCP-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- KDQPMQNHVQVVMR-UHFFFAOYSA-N 2-methyl-4-nitrophenol Chemical compound CC1=CC([N+]([O-])=O)=CC=C1O KDQPMQNHVQVVMR-UHFFFAOYSA-N 0.000 description 1
- AQDKZPFDOWHRDZ-UHFFFAOYSA-N 2-methyl-6-nitrophenol Chemical compound CC1=CC=CC([N+]([O-])=O)=C1O AQDKZPFDOWHRDZ-UHFFFAOYSA-N 0.000 description 1
- SYDNSSSQVSOXTN-UHFFFAOYSA-N 2-nitro-p-cresol Chemical compound CC1=CC=C(O)C([N+]([O-])=O)=C1 SYDNSSSQVSOXTN-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- BQEXDUKMTVYBRK-UHFFFAOYSA-N 4-methyl-3-nitrophenol Chemical compound CC1=CC=C(O)C=C1[N+]([O-])=O BQEXDUKMTVYBRK-UHFFFAOYSA-N 0.000 description 1
- PIIZYNQECPTVEO-UHFFFAOYSA-N 4-nitro-m-cresol Chemical compound CC1=CC(O)=CC=C1[N+]([O-])=O PIIZYNQECPTVEO-UHFFFAOYSA-N 0.000 description 1
- NQXUSSVLFOBRSE-UHFFFAOYSA-N 5-methyl-2-nitrophenol Chemical compound CC1=CC=C([N+]([O-])=O)C(O)=C1 NQXUSSVLFOBRSE-UHFFFAOYSA-N 0.000 description 1
- AOFFHYFFVWZNDG-UHFFFAOYSA-N ClC1=C(C=CC(=C1)C)OP(=O)(OC1=C(C=C(C=C1)C)Cl)OC1=C(C=C(C=C1)C)Cl Chemical compound ClC1=C(C=CC(=C1)C)OP(=O)(OC1=C(C=C(C=C1)C)Cl)OC1=C(C=C(C=C1)C)Cl AOFFHYFFVWZNDG-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Definitions
- esters of phenol as for example the esters of phenol with benzene sulfonic acid, and p-toluene sulfonic acid and aand B-naphthalene sulfonic acid, yield almost exclusively the corresponding p-nitrophenol ester which may be saponified to produce p-nitrophenol.
- a process for the production of substituted nitrophenols which comprises converting a substituted phenol into its phosphoric acid ester, nitrating said phosphoric acid ester and saponifying the nitro esters thus obtained to form a substituted mor p-nitrophenol.
- the phosphoric acid esters serving as the starting material for the process of the invention may easily be obtained by reacting 3 mols of the substituted phenol with 1 mol of phosphoryl chloride.
- An attractive feature of the phosphoric acid esters is that they are more soluble in the conventional nitrating mixtures than the esters of the substituted phenols with other acids.
- Example 1 143.2 grams /a mol) tris-(pchlorophenyl)-pl1osphate (M.P. 112 C.) are dissolved at 0-10 C. in 400 cc. of sulfuric acid. While cooling and stirring, 190 grams of a mixture consisting of 33% of nitric acid and 67% of sulfuric acid are then added dropwise at such a rate as to maintain the temperature between 5 and +10 C. Upon stirring the reaction mixture 4 hours at 20 C. it is poured into 1 liter of water. The aqueous mixture thus obtained is steam distilled until all the 2-nitro-4-chlorophenol formed has passed over.
- Example 2 143.2 grams /3 mol) of tris-(m-chlorophenyl)-phosphate (B.P. 230 C./0.04n1m.) are dissolved in 180 cc. of 96% sulfuric acid at a temperature below 10 C. To the solution there are added drop'wise at 5 l0 C. 1.90 grams of -a mixture consisting of 33% of nitric acid and 67% of sulfuric acid while cooling and stirring. Upon stirring for 3 hours at 20 C. the mixture is poured into 500 cc. of water and then steam distilled. 19.9 grams (11.5%) of 6-nitro-3-chlorophenol, M.P. 41.5 C., go over along with 3 liters of Water.
- Example 3 471.5 grams (1 mol) of tris-(2-chloro-4-methyl phenyl)-phosphate (M.P. 106 C.) are dissolved at a temperature below 15 C. in 1,500 cc. of 100% sulfuric acid and nitrated at -10 C. with 570 grams of a mixture consisting of 33% of nitric acid and 67% of sulfuric acid. Upon stirring for 6 hours at 20 C. the reaction mixture is poured into 2 liters of water. The resulting mixture is refluxed for 4 hours. On cooling 2-chloro-4-methyl-5-nitrophenol crystallizes. The crystals are filtered off with suction, washed with water and dried. Yield: 580 grams (97.7%). MP. 96-98 C. The product may be purified by sublimation or via its poorly soluble ammonium salt. Melting point upon purification: 101.5 C.
- the isomeric 2-chloro-4-rnethyl-6-nitropheno1 is not formed in an appreciable amount.
- Process for the production of substituted nitrophenols which comprises converting a phenol selected from the group consisting of mono-substituted phenols substituted in one of the mand p-positions and disubstituted phenols substituted in one of the o-positions and the p-position with substituents selected from the group consisting of chlorine and methyl groups into its phosphoric acid ester, nitrating said phosphoric acid ester in the presence of at least 96% sulfuric acid and sap onifying the nitration product to form a substituted nitrophenol containing a substantial quantity of the substituted m-nitrophenol free from a substantial quantity of the substituted o-nitrophenol.
- Process for the production of 4-nitro-3-chlorophenol which comprises converting m-chlorophenol into tris-(m-chlorophenyl)-phosphate, nitrating tris-(m-chlorophenyl) phosphate, saponifying the nitration product and recovering 4-nitro-3-chlorophenol.
- Process for the production of 2-chloro-4-methyl- S-nitrophenol which comprises converting 2-chloro4- methyl phenol into tris-(2-ch10ro-4-methyl phenyl)-phosphate, nitrating tns-(2-chloro-4-methyl phenyD-phosphate, saponifying the nitration product and recovering 2-chloro- 4-methyl-5-nitrophenol.
- Process for the production of substituted nitrophenols which comprises nitrating a phosphoric acid ester of a phenol selected from the group consisting of monosubstituted phenols substituted in one of the m-, 0-, and p-positions and di-substituted phenols substituted in two of the m-, oand p-positions with substituents selected from the group consisting of chlorine and methyl groups in the presence of at least 96% sulfuric acid, and saponifying the nitration product to form a substituted nitrophenol containing a substantial quantity of the substituted m-nitrophenol free from a substantial quantity of the substituted o-nitrophenol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States PRODUCTION OF SUBSTITUTED NITROPHENOLS No Drawing. Filed Sept. 8, 1954, Ser. No. 454,818 Claims priority, application Germany Sept. 9, 1953 8 Claims. (Cl. 260-622) This invention relates to a process for the production of substituted nitrophenols.
It is well known that in the nitration of phenol a mixture of p-nitrophenol and o-nitrophenol is obtained. In contrast thereto, certain esters of phenol, as for example the esters of phenol with benzene sulfonic acid, and p-toluene sulfonic acid and aand B-naphthalene sulfonic acid, yield almost exclusively the corresponding p-nitrophenol ester which may be saponified to produce p-nitrophenol.
In the nitration of esters of substituted phenols the pand m-position, respectively, are much less fa'vored, substantial amounts of the corresponding o-nitrophenol ester being formed.
It is an object of the present invention to provide a process for the production of substituted mand p-nitrophenols. Another object is to provide a process for the production of substituted nitrophenols in which only a small amount of the o-nitro derivative is formed. A further object is to provide a process for the production of 4-nitro-3-chlorop-henol. Still further objects will become apparent hereinafter.
Very surprisingly, it has now been found that in the nitration of esters of substituted phenols the phosphoric acid esters basically dilfer from the other esters. While the esters of substituted phenols with carbonic acid, acetic acid, benzene sulfonic acid, etc. yield considerable amounts of the corresponding o-nitro derivative in addition to the mor p-nitro derivative, the phosphoric acid esters of substituted phenols form only small amounts of the corresponding o-nitro derivative, the main product being the mor the p-nitro compound.
Thus, in accordance with the present invention there is provided a process for the production of substituted nitrophenols which comprises converting a substituted phenol into its phosphoric acid ester, nitrating said phosphoric acid ester and saponifying the nitro esters thus obtained to form a substituted mor p-nitrophenol.
The following experimental rmults are given to illustrate the invention:
By nitration of o-cresyl phosphate and subsequent saponification there are obtained 99% of 4-nitro-2-methylphenol and only 1% of 6-nitro-2-methyl phenol.
The results obtained in the nitration of various esters of m-chlorophenol are shown in the following table:
As may be seen from the table, in the case of the atnt 0* 2,985,688 Patented May 23, 1961 ice phosphoric ester the smallest amount of the onitro derivative (6-nitro-3-chlorophenol) is formed while the p-nitro compound (4-nitro-3-chlorophenol) is produced in a maximum yield.
By nitration of m-cresyl phosphate and subsequent saponification there are obtained 1.5% of 6-nitro-3- methyl phenol and 98.5% of 4-nitro-3-methyl phenol.
The nitration of phosphoric acid esters of phenols carrying an ortho-para-directing substituent in the p-position results largely in the formation of the corresponding m-nitro compound, while the o-nitro derivative is obtained only in a small amount. Thus, by nitrating p-chlorophenyl phosphate and saponifying the nitration product there are obtained 70.5% of 3-nitro-4-chlorophenol and 29.5% of 2-nitm-4-chlorophenol. From p-cresyl phosphate there are obtained 97% of 3-nitro-4-methyl phenol and 3% of 2-nitro-4-methyl phenol.
The nitration of phosphoric acid esters of phenols carrying ortho-para-directing substituents in the oand p-position, as for example 2,4-dichlorophenol, 4-chloro- Z-methyl phenol and 4-methyl-2-chlorophenol, gives rise almost exclusively to the formation of the corresponding m-nitro compound, the o'-nitro derivative being produced only in a negligible amount.
The phosphoric acid esters serving as the starting material for the process of the invention may easily be obtained by reacting 3 mols of the substituted phenol with 1 mol of phosphoryl chloride. An attractive feature of the phosphoric acid esters is that they are more soluble in the conventional nitrating mixtures than the esters of the substituted phenols with other acids.
The method of the present invention will be apparent to those skilled in the art from a consideration of the following examples, which are illustrative only and are in no way to be construed as limiting:
Example 1 143.2 grams /a mol) tris-(pchlorophenyl)-pl1osphate (M.P. 112 C.) are dissolved at 0-10 C. in 400 cc. of sulfuric acid. While cooling and stirring, 190 grams of a mixture consisting of 33% of nitric acid and 67% of sulfuric acid are then added dropwise at such a rate as to maintain the temperature between 5 and +10 C. Upon stirring the reaction mixture 4 hours at 20 C. it is poured into 1 liter of water. The aqueous mixture thus obtained is steam distilled until all the 2-nitro-4-chlorophenol formed has passed over. From the distillate there are recovered 50.7 grams (29.2%) of 2-nitro-4-chlorophenol melting at 87 C. The residue from the steam distillation is cooled, whereby crude 3-nitro-4-chlorophenol is crystallized. The product is filtered off by suction, washed with water and dried. Yield of 3-nitro-4-chlorophenol: 122 grams (70.3%). M.P. (upon recrystallization from benzene): 126.5 C.
Example 2 143.2 grams /3 mol) of tris-(m-chlorophenyl)-phosphate (B.P. 230 C./0.04n1m.) are dissolved in 180 cc. of 96% sulfuric acid at a temperature below 10 C. To the solution there are added drop'wise at 5 l0 C. 1.90 grams of -a mixture consisting of 33% of nitric acid and 67% of sulfuric acid while cooling and stirring. Upon stirring for 3 hours at 20 C. the mixture is poured into 500 cc. of water and then steam distilled. 19.9 grams (11.5%) of 6-nitro-3-chlorophenol, M.P. 41.5 C., go over along with 3 liters of Water.
From the residue of the steam distillation 4-nitro-3- chlorophenol crystallizes upon cooling. The product is filtered off by suction, Washed with water and dried. Yield: 150.5 grams (86.8%). Upon recrystallization from benzene there are obtained 131.5 grams (75.8%) of 4-nitro-3-chlorophenol melting at 124.5 C.
3 Example 3 471.5 grams (1 mol) of tris-(2-chloro-4-methyl phenyl)-phosphate (M.P. 106 C.) are dissolved at a temperature below 15 C. in 1,500 cc. of 100% sulfuric acid and nitrated at -10 C. with 570 grams of a mixture consisting of 33% of nitric acid and 67% of sulfuric acid. Upon stirring for 6 hours at 20 C. the reaction mixture is poured into 2 liters of water. The resulting mixture is refluxed for 4 hours. On cooling 2-chloro-4-methyl-5-nitrophenol crystallizes. The crystals are filtered off with suction, washed with water and dried. Yield: 580 grams (97.7%). MP. 96-98 C. The product may be purified by sublimation or via its poorly soluble ammonium salt. Melting point upon purification: 101.5 C.
The isomeric 2-chloro-4-rnethyl-6-nitropheno1 is not formed in an appreciable amount.
While the above description points out the preferred embodiments of our invention, it is to be understood that departures may be made therefrom within the scope of the invention as described and claimed.
We claim:
1. Process for the production of substituted nitrophenols, which comprises converting a phenol selected from the group consisting of mono-substituted phenols substituted in one of the mand p-positions and disubstituted phenols substituted in one of the o-positions and the p-position with substituents selected from the group consisting of chlorine and methyl groups into its phosphoric acid ester, nitrating said phosphoric acid ester in the presence of at least 96% sulfuric acid and sap onifying the nitration product to form a substituted nitrophenol containing a substantial quantity of the substituted m-nitrophenol free from a substantial quantity of the substituted o-nitrophenol.
2. Process in accordance with claim 1, in which said phosphoric acid ester is obtained by reacting a substituted phenol with phosphoryl chloride.
3. Process in accordance with claim 1, in which said saponification is carried out by heating the nitration product with Water.
4. Process for the production of 3-nitro-4-chlorophenol, which comprises converting p-chlorophenol into tris-(p-chlorophenyl)-phosphate, nitrating tris-(p-chlorophenyl) -phosphate, saponifying the nitration product and recovering 3-nitro-4-chlorophenol.
5. Process for the production of 4-nitro-3-chlorophenol, which comprises converting m-chlorophenol into tris-(m-chlorophenyl)-phosphate, nitrating tris-(m-chlorophenyl) phosphate, saponifying the nitration product and recovering 4-nitro-3-chlorophenol.
6. Process for the production of 2-chloro-4-methyl- S-nitrophenol, which comprises converting 2-chloro4- methyl phenol into tris-(2-ch10ro-4-methyl phenyl)-phosphate, nitrating tns-(2-chloro-4-methyl phenyD-phosphate, saponifying the nitration product and recovering 2-chloro- 4-methyl-5-nitrophenol.
7. Process for the production of substituted nitrophenols which comprises nitrating a phosphoric acid ester of a phenol selected from the group consisting of monosubstituted phenols substituted in one of the m-, 0-, and p-positions and di-substituted phenols substituted in two of the m-, oand p-positions with substituents selected from the group consisting of chlorine and methyl groups in the presence of at least 96% sulfuric acid, and saponifying the nitration product to form a substituted nitrophenol containing a substantial quantity of the substituted m-nitrophenol free from a substantial quantity of the substituted o-nitrophenol.
8. Process for the production of 4-nitro-3-chlorophenol which comprises nitrating tris-(m-chlorophenyl)-phosphate, saponifying the nitration product and recovering the 4-nitro-3-chlorophenol formed.
References Cited in the file of this patent Rapp: Annalen der Chemie, vol. 224 (1884), pp. 172-178 (7 pages), entire article pp. 156-178.
Hoeflake: Chem. Abstracts, vol. 11 (1917), pp. 42-45 (4 pages).
Ketelaar et al.: Rec. Trav. Chim., vol. 71 (1952), pp. 1253-8 (6 pages).
Claims (1)
1. PROCESS FOR THE PRODUCTION OF SUBSTITUTED NITROPHENOLS, WHICH COMPRISES CONVERTING A PHENOL SELECTED FROM THE GROUP CONSISTING OF MONO-SUBSTITUTED PHENOLS SUBSTITUTED IN ONE OF THE M- AND P-POSITIONS AND DISUBSTITUTED PHENOLS SUBSTITUTED IN ONE OF THE O-POSITIONS AND THE P-POSITION WITH SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND METHYL GROUPS INTO ITS PHOSPHORIC ACID ESTER, NITRATING SAID PHOSPHERIC ACID ESTER IN THE PRESENCE OF AT LEAST 96% SULFURIC ACID AND SAPONIFYING THE NITRATION PRODUCT TO FORM A SUBSTITUTED NITROPHENOL CONTAINING A SUBSTANTIAL QUANTITY OF THE SUBSTITUTED M-NITROPHENOL FREE FROM A SUBSTANTIAL QUANTITY OF THE SUBSTITUTED O-NITROPHENOL.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2985688X | 1953-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2985688A true US2985688A (en) | 1961-05-23 |
Family
ID=8067472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US454818A Expired - Lifetime US2985688A (en) | 1953-09-09 | 1954-09-08 | Production of substituted nitrophenols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2985688A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215722A (en) * | 1960-12-27 | 1965-11-02 | Dow Chemical Co | Process for preparing p-chlorophenyl borates |
| US3416911A (en) * | 1965-12-09 | 1968-12-17 | Chemagro Corp | Method of defoliating and desiccating plants with substituted triphenyl phosphates and phosphites |
| US3669998A (en) * | 1966-06-21 | 1972-06-13 | Kureha Chemical Ind Co Ltd | Chloro-nitro substituted phenyl esters of aliphatic acids |
| US3987113A (en) * | 1975-06-13 | 1976-10-19 | Sumitomo Chemical Company, Limited | Preparation of 5-methyl-2-nitrophenol |
| US4034050A (en) * | 1975-01-13 | 1977-07-05 | Sumitomo Chemical Company, Ltd. | Preparation of 5-methyl-2-nitrophenol |
| US4101569A (en) * | 1975-11-03 | 1978-07-18 | Bayer Aktiengesellschaft | Process for the preparation of 4,4'-dinitrodiphenyl carbonate |
-
1954
- 1954-09-08 US US454818A patent/US2985688A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215722A (en) * | 1960-12-27 | 1965-11-02 | Dow Chemical Co | Process for preparing p-chlorophenyl borates |
| US3416911A (en) * | 1965-12-09 | 1968-12-17 | Chemagro Corp | Method of defoliating and desiccating plants with substituted triphenyl phosphates and phosphites |
| US3669998A (en) * | 1966-06-21 | 1972-06-13 | Kureha Chemical Ind Co Ltd | Chloro-nitro substituted phenyl esters of aliphatic acids |
| US4034050A (en) * | 1975-01-13 | 1977-07-05 | Sumitomo Chemical Company, Ltd. | Preparation of 5-methyl-2-nitrophenol |
| US3987113A (en) * | 1975-06-13 | 1976-10-19 | Sumitomo Chemical Company, Limited | Preparation of 5-methyl-2-nitrophenol |
| US4101569A (en) * | 1975-11-03 | 1978-07-18 | Bayer Aktiengesellschaft | Process for the preparation of 4,4'-dinitrodiphenyl carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2985688A (en) | Production of substituted nitrophenols | |
| US4400530A (en) | Process for preparing substituted diphenyl ethers | |
| US2450386A (en) | Manufacture of compounds containing amidine groups | |
| US2207727A (en) | Nitro-tertiary-alkyl-phenols | |
| US3519693A (en) | Nitration process for phenolic compounds | |
| US3868418A (en) | Novel N-(ortho- and para-nitrobenzoyl)-sulfoximine intermediates and process for their production | |
| US2948756A (en) | Terephthalaldehyde preparation | |
| US2170996A (en) | Ethylene glycol di-(aryloxyacetates) | |
| US2421165A (en) | Process for preparing nitro amines | |
| US3517075A (en) | Nitration of phenol using recycle acid | |
| US3140319A (en) | Preparation of p-nitrohalobenzenes | |
| US2850537A (en) | Process for making 3-halo-4-nitrophenols | |
| US3673123A (en) | 2,2{40 ,4,4{40 -tetrachloro-5,5{40 -diamino-diphenyl ether | |
| US2698329A (en) | Trimethylenedioxybenzene and certain derivatives thereof | |
| US2681364A (en) | Process for the production of 1-p-nitrophenyl-2-acylamidopropane-1,3-diols | |
| Morton et al. | The Metalation of Isopropylbenzene, Condensations by Sodium. XXIX | |
| US2948725A (en) | Flow sheet-process | |
| US3130218A (en) | Process for the preparation of 4-nitrostilbene carbonitriles | |
| US2406504A (en) | Nitro ketals and process for preparation thereof | |
| US3287396A (en) | Phenyldesoxythyronines | |
| US2991315A (en) | Method of nitrating terminal nitromethyl groups | |
| US2481283A (en) | Preparation of nitratoalkyl nitramines | |
| US2768217A (en) | 2-and 4-methyl-5-nitro-alpha1, alpha3-xylylene dichlorides and their preparation | |
| US4038284A (en) | N-acylation of oxazolidines | |
| Cady et al. | Freezing points of the system water-trifluoroacetic acid |