GB2055799A - Improved method for the preparation of meta-phenoxy-benzaldehyde - Google Patents

Improved method for the preparation of meta-phenoxy-benzaldehyde Download PDF

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Publication number
GB2055799A
GB2055799A GB7927582A GB7927582A GB2055799A GB 2055799 A GB2055799 A GB 2055799A GB 7927582 A GB7927582 A GB 7927582A GB 7927582 A GB7927582 A GB 7927582A GB 2055799 A GB2055799 A GB 2055799A
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meta
benzaldehyde
dioxolane
phenoxy
preparation
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GB2055799B (en
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Produits Chimiques Auxiliaires et de Synthese
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Produits Chimiques Auxiliaires et de Synthese
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for the preparation of meta-phenoxy-benzaldehyde comprises reacting an excess of phenol with meta-bromo-benzaldehyde dioxolane at 200 DEG C in the presence of copper or of a copper salt and potassium carbonate, and then eliminating the dioxolane function by means of a strong acid. This method is short and yields a product of high purity which can be used as e.g. an intermediate for insecticides.

Description

SPECIFICATION Improved method for the preparation of meta-phenoxy-benzaldehyde This invention relates to an improved method for the preparation of meta-phenoxy-benzaldehyde. This compound is useful as an intermediate in the synthesis of various products, such as insecticides.
Several methods of preparation are known already. Nevertheless, the methods of the prior art have the draw-back of poor yields, or to entail too many expenses.
The invention has for its object a method for the preparation of meta-phenoxy-benzaldehyde which is cheap, has a high yield and is using simple implements.
The method according to the invention is characterized in that the dioxolane salt of meta-bromobenzaldehyde is reacted at 2000C, in presence of copper or a copper salt and potassium carbonate with phenol in excess, and then the dioxolane function is finally eliminated by hydrochloric acid. (This latter step is a method known per se, the dioxolane group is used for the protection of the aldehyde function during the reaction). The above indicated temperature (200"C) is given as an optimum, and practically, acceptable results may be obtained in the range of 170 to 21 0 C.
The method according to the invention may be represented by the following developped formula (see next page).
The method according to the invention affords the advantages to be short, and to yield a product of a high purity, what gives much importance to said method. The chemical yield is in the range of 60%.
The meta-bromo-benzaldehyde is obtained according to the methods described in the literature (Organic preparations and procedures, Int. 1974,6,251-3). The dioxolane is also prepared according to conventional methods.
The invention will be more fully understood by reference to the following detailed example.
In a tricol of one liter, fitted with an agitation device, a thermometer and an apparatus of the Dean-Stark type, 103.49 (0.45 mole) of meta-bromo-benzaldehyde dioxolane, 113 g of phenol (1.2 mole), 91 g of potassium carbonate (0.66 mole) and 1 g of copper powder are mixed.
The mixture is gradually heated to 200"C in the whole mass, while water formed by the reaction is being separated by distillation, at the same time as a portion of the phenol in excess.
This temperature is maintained for one hour, then the reaction mixture is cooled to a temperature of about 90"C. 200 ml water is added and after that, 150 ml of hydrochloric acid is carefully added. After completion of the addition, the mixture is refluxed for about 30 minutes.
The temperature is lowered to about 20"C and the solution is filtered for eliminating copper salts, and extracted several times with an organic solvent such as methylene chloride. The organic phases are mixed, washed with water until neutrality, dried on sodium sulphate and distillated.
The meta-phenoxy-benzaldehyde distillates between 180-185"C under 15 mm Hg. 62 g is obtained, i.e. the yield is 70% with a purity dosed by CPV of 98% minimum.
1. A method for the preparation of meta-phenoxy-benzaldehyde wherein as excess of phenol and the meta-bromo-benzaldehyde dioxolane are made to react together at about 200"C, in the presence of copper or of a copper salt and potassium carbonate and after that the dioxolane function is eliminated by a strong acid.
2. A method for the preparation of meta-phenoxy-benzaldehyde substantially as herein before described.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (2)

**WARNING** start of CLMS field may overlap end of DESC **. SPECIFICATION Improved method for the preparation of meta-phenoxy-benzaldehyde This invention relates to an improved method for the preparation of meta-phenoxy-benzaldehyde. This compound is useful as an intermediate in the synthesis of various products, such as insecticides. Several methods of preparation are known already. Nevertheless, the methods of the prior art have the draw-back of poor yields, or to entail too many expenses. The invention has for its object a method for the preparation of meta-phenoxy-benzaldehyde which is cheap, has a high yield and is using simple implements. The method according to the invention is characterized in that the dioxolane salt of meta-bromobenzaldehyde is reacted at 2000C, in presence of copper or a copper salt and potassium carbonate with phenol in excess, and then the dioxolane function is finally eliminated by hydrochloric acid. (This latter step is a method known per se, the dioxolane group is used for the protection of the aldehyde function during the reaction). The above indicated temperature (200"C) is given as an optimum, and practically, acceptable results may be obtained in the range of 170 to 21 0 C. The method according to the invention may be represented by the following developped formula (see next page). The method according to the invention affords the advantages to be short, and to yield a product of a high purity, what gives much importance to said method. The chemical yield is in the range of 60%. The meta-bromo-benzaldehyde is obtained according to the methods described in the literature (Organic preparations and procedures, Int. 1974,6,251-3). The dioxolane is also prepared according to conventional methods. The invention will be more fully understood by reference to the following detailed example. In a tricol of one liter, fitted with an agitation device, a thermometer and an apparatus of the Dean-Stark type, 103.49 (0.45 mole) of meta-bromo-benzaldehyde dioxolane, 113 g of phenol (1.2 mole), 91 g of potassium carbonate (0.66 mole) and 1 g of copper powder are mixed. The mixture is gradually heated to 200"C in the whole mass, while water formed by the reaction is being separated by distillation, at the same time as a portion of the phenol in excess. This temperature is maintained for one hour, then the reaction mixture is cooled to a temperature of about 90"C. 200 ml water is added and after that, 150 ml of hydrochloric acid is carefully added. After completion of the addition, the mixture is refluxed for about 30 minutes. The temperature is lowered to about 20"C and the solution is filtered for eliminating copper salts, and extracted several times with an organic solvent such as methylene chloride. The organic phases are mixed, washed with water until neutrality, dried on sodium sulphate and distillated. The meta-phenoxy-benzaldehyde distillates between 180-185"C under 15 mm Hg. 62 g is obtained, i.e. the yield is 70% with a purity dosed by CPV of 98% minimum. CLAIMS
1. A method for the preparation of meta-phenoxy-benzaldehyde wherein as excess of phenol and the meta-bromo-benzaldehyde dioxolane are made to react together at about 200"C, in the presence of copper or of a copper salt and potassium carbonate and after that the dioxolane function is eliminated by a strong acid.
2. A method for the preparation of meta-phenoxy-benzaldehyde substantially as herein before described.
GB7927582A 1979-08-08 1979-08-08 Method for the preparation of metaphenoxy-benzaldehyde Expired GB2055799B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB7927582A GB2055799B (en) 1979-08-08 1979-08-08 Method for the preparation of metaphenoxy-benzaldehyde

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7927582A GB2055799B (en) 1979-08-08 1979-08-08 Method for the preparation of metaphenoxy-benzaldehyde

Publications (2)

Publication Number Publication Date
GB2055799A true GB2055799A (en) 1981-03-11
GB2055799B GB2055799B (en) 1983-05-11

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GB7927582A Expired GB2055799B (en) 1979-08-08 1979-08-08 Method for the preparation of metaphenoxy-benzaldehyde

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185016A (en) * 1985-12-20 1987-07-08 Hardwicke Chemical Co Process for preparing 3-phenoxybenzaldehydes and their acetals
US4691033A (en) * 1985-12-20 1987-09-01 Hardwicke Chemical Company Process for preparing 3-phenoxybenzaldehydes
EP0289669A1 (en) * 1987-05-05 1988-11-09 Hardwicke Chemical Company Process for preparing 3-phenoxybenzaldehydes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2185016A (en) * 1985-12-20 1987-07-08 Hardwicke Chemical Co Process for preparing 3-phenoxybenzaldehydes and their acetals
US4691033A (en) * 1985-12-20 1987-09-01 Hardwicke Chemical Company Process for preparing 3-phenoxybenzaldehydes
GB2185016B (en) * 1985-12-20 1989-11-29 Hardwicke Chemical Co Process for preparing 3-phenoxybenzaldehydes
EP0289669A1 (en) * 1987-05-05 1988-11-09 Hardwicke Chemical Company Process for preparing 3-phenoxybenzaldehydes

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Publication number Publication date
GB2055799B (en) 1983-05-11

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