CA1069135A - Process for the preparation of 3-bromobenzaldehyde - Google Patents
Process for the preparation of 3-bromobenzaldehydeInfo
- Publication number
- CA1069135A CA1069135A CA251,701A CA251701A CA1069135A CA 1069135 A CA1069135 A CA 1069135A CA 251701 A CA251701 A CA 251701A CA 1069135 A CA1069135 A CA 1069135A
- Authority
- CA
- Canada
- Prior art keywords
- benzaldehyde
- bromine
- chlorine
- mixture
- 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
Links
Classifications
-
- 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
- C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A B S T R A C T
A process for the preparation of 3-bromobenzaldehyde which comprises brominating benzaldehyde at a temperature below 100°C in the presence of a chlorinated hydrocarbon solvent and a bromination catalyst, the molar ratio of bromination catalyst to benzaldehyde being at least 1:1, wherein the bromination is carried out using a mixture of chlorine and bromine.
A process for the preparation of 3-bromobenzaldehyde which comprises brominating benzaldehyde at a temperature below 100°C in the presence of a chlorinated hydrocarbon solvent and a bromination catalyst, the molar ratio of bromination catalyst to benzaldehyde being at least 1:1, wherein the bromination is carried out using a mixture of chlorine and bromine.
Description
This invention relates to a process for the preparation of 3-bromobenzaldehyde by the bromination of benzaldehyde.
It is known from J.Org.Chem. 1958, 23, 1412-9 that bromine reacts -with benzaldehyde at a molar ratio of bromine to benzaldehyde of 1.1:1, in the presence of aluminium chloride and in the absence of a solvent, to give 3-bromobenzaldehyde in 52% yield. When a solvent is used, as described in "Organic Preparations and Procedures Int." 1974, 6, 251-3, the yield of 3-bromobenzaldehyde is 75%. In these known procedures one mol of bromine is consumed per mol of benzaldehyde and one mol of hydrogen bromide is evolved per mol of 3-bromobenzaldehyde.
The process of the invention consumes less bromine per mol of benzaldehyde and gives 3-bromobenzaldehyde in higher yield compared with the known procedures.
Accordingly the present invention provides a process for the preparation of 3-bromobenzaldehyde which comprises brominating benzaldehyde at a temperature in the range of 0C to 50C in the presence of a chlorinated hydrocarbon solvent and a Lewis acid bromination catalyst, the molar ratio of bromination catalyst to benzaldehyde being at least 1:1, wherein the bromination is carried out using a mixture of chlorine and bromine wherein the molar ratio of chlorine to bromine is from 0.9:1 to 1:1.
The chlorine and bromine may be mixed before they are brought into contact with the benzaldehyde, bromination catalyst and solvent. For example, the two halogens may be mixed in the chlorinated hydrocarbon solvent, and the resulting solution added to a mixture of benzaldehyde, bromination catalyst and solvent. The mixture of chlorine and bromine may also be formed in-situ.
Thus, chlorine and bromine may be introduced simultaneously but separately into a mixture of benzaldehyde, bromination catalyst and solvent. Alternative-ly chlorine may be introduced, for example, over a period of 1 to 5 hours, into a mixture of benzaldehyde, bromination catalyst, bromine and solvent.
The bromination catalyst is preerably a Lewis acid such as
It is known from J.Org.Chem. 1958, 23, 1412-9 that bromine reacts -with benzaldehyde at a molar ratio of bromine to benzaldehyde of 1.1:1, in the presence of aluminium chloride and in the absence of a solvent, to give 3-bromobenzaldehyde in 52% yield. When a solvent is used, as described in "Organic Preparations and Procedures Int." 1974, 6, 251-3, the yield of 3-bromobenzaldehyde is 75%. In these known procedures one mol of bromine is consumed per mol of benzaldehyde and one mol of hydrogen bromide is evolved per mol of 3-bromobenzaldehyde.
The process of the invention consumes less bromine per mol of benzaldehyde and gives 3-bromobenzaldehyde in higher yield compared with the known procedures.
Accordingly the present invention provides a process for the preparation of 3-bromobenzaldehyde which comprises brominating benzaldehyde at a temperature in the range of 0C to 50C in the presence of a chlorinated hydrocarbon solvent and a Lewis acid bromination catalyst, the molar ratio of bromination catalyst to benzaldehyde being at least 1:1, wherein the bromination is carried out using a mixture of chlorine and bromine wherein the molar ratio of chlorine to bromine is from 0.9:1 to 1:1.
The chlorine and bromine may be mixed before they are brought into contact with the benzaldehyde, bromination catalyst and solvent. For example, the two halogens may be mixed in the chlorinated hydrocarbon solvent, and the resulting solution added to a mixture of benzaldehyde, bromination catalyst and solvent. The mixture of chlorine and bromine may also be formed in-situ.
Thus, chlorine and bromine may be introduced simultaneously but separately into a mixture of benzaldehyde, bromination catalyst and solvent. Alternative-ly chlorine may be introduced, for example, over a period of 1 to 5 hours, into a mixture of benzaldehyde, bromination catalyst, bromine and solvent.
The bromination catalyst is preerably a Lewis acid such as
-2-~;
\ 1069~35 aluminium chloride or ferric chloride. The molar ratio of bromination catalyst to benzaldehyde is preferably from 1:1 to 1.5:1, in particular from 1.2:1 to 1.35:1.
The molar ratio of bromine to benzaldehyde is preferably from 0.5:1 to 0.6:1, i.e. the stoichiometric amount or a small excess of bromine is preferably used. The molar ratio of chlorine to bromine used is as indicated above from 0.90:1 to 1:1, i.e. approximately equimolar amounts of each halogen are used.
The chlorinated hydrocarbon solvent is preferably a chlorinated (cyclo)alkane of up to 6 carbon atoms such as 1,2-dichloroethane, dichlorome-thane, chloroform, carbon tetrachloride or chlorocyclohexene. 1,2-Dichloroe-thane is particularly preferred. The starting concentration of benzaldehyde in the solvent is preferably from 2 to 7 mol per litre, in particular 2 to 6 mol per litre.
The temperature of the bromination is preferably from 10 to 25C.
\ 1069~35 aluminium chloride or ferric chloride. The molar ratio of bromination catalyst to benzaldehyde is preferably from 1:1 to 1.5:1, in particular from 1.2:1 to 1.35:1.
The molar ratio of bromine to benzaldehyde is preferably from 0.5:1 to 0.6:1, i.e. the stoichiometric amount or a small excess of bromine is preferably used. The molar ratio of chlorine to bromine used is as indicated above from 0.90:1 to 1:1, i.e. approximately equimolar amounts of each halogen are used.
The chlorinated hydrocarbon solvent is preferably a chlorinated (cyclo)alkane of up to 6 carbon atoms such as 1,2-dichloroethane, dichlorome-thane, chloroform, carbon tetrachloride or chlorocyclohexene. 1,2-Dichloroe-thane is particularly preferred. The starting concentration of benzaldehyde in the solvent is preferably from 2 to 7 mol per litre, in particular 2 to 6 mol per litre.
The temperature of the bromination is preferably from 10 to 25C.
3-Bromobenzaldehyde is an intermediate for the preparation of 3-phenoxybenzyl alcohol derivatives which form insecticidally active esters with certain carboxylic acids.
The invention is illustrated further in the following Examples.
EXAMPLE I
Chlorine (0.5 mol) was added to a solution of bromine (0.5 mol) in 1,2-dichloroethane (20 ml) cooled in a solid C02/isopropanol bath and the resulting solution was made up to 100 ml with more 1,2-dichloroethane. This solution was added over a period of 2 hours 20 minutes to a mixture of aluminium chloride (1.3 mol) and benzaldehyde (1.0 mol) in 1,2-dichloroethane ~200 ml) maintained at 23 to 25C. The mixture was then stirred for a further one hour at this temperature. At this stage the conversion of benzalde-hyde was 89% and the selectivity to 3-bromobenzaldehyde was 95 to 96% as shown by GLC.
3~ The re~ction mixture was diluted with sufficient water to redissolve the initial precipitate of aluminium hydroxide. The organic layer was then separated, washed with water ~100 ml) and dried (MgS04). The solvent ~ 1 - . .. . . .
-`` ~` ,,3,~ 1069135 was then removed and the residue was fractionally distilled to give 3-bromobenzalde}lyde, b.p. 80C
at 1.5 mm Hg.
EXAMPLE II
Benzaldehyde (1.3 mol) was added over a period of 0.75 hour to a mixture of alum:inium chloride (1.43 mol) and 1,2-dichloroethane (500 ml) at 22C. Liquid bromine (0.65 mol) was then added to the mixture at 15C. Gaseous chlorine was then passed into the mixture at 15C over a period of two hours to give a chlorine to bromine molar ratio of 0.95:1. The mixture was then stirred for a further one hour at 15C. A solution ; of formic acid (0.0355 mol) in water (500 ml) was added to the mixture to destroy excess bromine. The organic phase was then washed first with water (500 ml) containing sodium thiosulphate to promote phase separation, and then with water (500 ml). The washings were combined and extracted with 1,2-dichloroethane ~250 ml). The two organic phases were then combined and analysed by GLC. The results are shown in the table.
EXAMPLES III to IX
These Examples were carried out in a similar manner to that o~ Example II. The reaction conditions and the results are shown in the Table.
.
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.
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ol ~ l l~
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I ~
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rl l N
01 m , "
s~l 11 ~dl I 11 01 ~ I .. .. .. .. .. .. .. .. ~, Io o o o oo o o 11 ~ 1~ 1~/ N N~~\~1 ~1 ~1 11 I ~ p~ I Il I CC I
~/ 1 1' P. I H
IH H P HH H X
X ~ IH H H p pp p H
The invention is illustrated further in the following Examples.
EXAMPLE I
Chlorine (0.5 mol) was added to a solution of bromine (0.5 mol) in 1,2-dichloroethane (20 ml) cooled in a solid C02/isopropanol bath and the resulting solution was made up to 100 ml with more 1,2-dichloroethane. This solution was added over a period of 2 hours 20 minutes to a mixture of aluminium chloride (1.3 mol) and benzaldehyde (1.0 mol) in 1,2-dichloroethane ~200 ml) maintained at 23 to 25C. The mixture was then stirred for a further one hour at this temperature. At this stage the conversion of benzalde-hyde was 89% and the selectivity to 3-bromobenzaldehyde was 95 to 96% as shown by GLC.
3~ The re~ction mixture was diluted with sufficient water to redissolve the initial precipitate of aluminium hydroxide. The organic layer was then separated, washed with water ~100 ml) and dried (MgS04). The solvent ~ 1 - . .. . . .
-`` ~` ,,3,~ 1069135 was then removed and the residue was fractionally distilled to give 3-bromobenzalde}lyde, b.p. 80C
at 1.5 mm Hg.
EXAMPLE II
Benzaldehyde (1.3 mol) was added over a period of 0.75 hour to a mixture of alum:inium chloride (1.43 mol) and 1,2-dichloroethane (500 ml) at 22C. Liquid bromine (0.65 mol) was then added to the mixture at 15C. Gaseous chlorine was then passed into the mixture at 15C over a period of two hours to give a chlorine to bromine molar ratio of 0.95:1. The mixture was then stirred for a further one hour at 15C. A solution ; of formic acid (0.0355 mol) in water (500 ml) was added to the mixture to destroy excess bromine. The organic phase was then washed first with water (500 ml) containing sodium thiosulphate to promote phase separation, and then with water (500 ml). The washings were combined and extracted with 1,2-dichloroethane ~250 ml). The two organic phases were then combined and analysed by GLC. The results are shown in the table.
EXAMPLES III to IX
These Examples were carried out in a similar manner to that o~ Example II. The reaction conditions and the results are shown in the Table.
.
.. ~. - .
.
-- ,6~ --gl~S
o a~ I "
~ o ;~
r1 h S I ~ ~
"
rl I ~ I
IJ J ~ ~IS~ J
O N I OC~
a) ~ I "
O I
~ o ~
O -r~
.
~ o l ~
ol ~ l l~
I ~ Io oIn mIno o o 11 ~11 0 I N N ~~lr~N 3 15~ 11 ~>! s I ,~
N I - .. .. .. .. .. .. ..
N mI ~ ~ o~o~
I ~
I C~ I O O O OO O 0 11 ~ l ll t~ I O 1 11 E-l I ~ 1 I C.)1 ~1 1~
rl l N
01 m , "
s~l 11 ~dl I 11 01 ~ I .. .. .. .. .. .. .. .. ~, Io o o o oo o o 11 ~ 1~ 1~/ N N~~\~1 ~1 ~1 11 I ~ p~ I Il I CC I
~/ 1 1' P. I H
IH H P HH H X
X ~ IH H H p pp p H
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 3-bromobenzaldehyde which comprises bromlnating benzaldehyde at a temperature in the range of 0°C to 50°C in the presence of a chlorinated hydrocarbon solvent and a Lewis acid bromination catalyst, the molar ratio of bromination catalyst to benzaldehyde being at least 1:1, wherein the bromination is carried out using a mixture of chlorine and bromine wherein the molar ratio of chlorine to bromine is from 0.9:1 to 1:1.
2. A process as claimed in claim 1 in which the chlorine and bromine are mixed before they are brought into contact with the benzaldehyde, bromination catalyst and solvent.
3. A process as claimed in claim 2 in which the mixture of chlorine and bromine is formed in the chlorinated hydrocarbon solvent.
4. A process as claimed in claim 1, in which the mixture of chlorine and bromine is formed in a mixture of benzaldehyde, bromination catalyst and solvent.
5. A process as claimed in claim 4, in which the chlorine and bromine are introduced simultaneously but separately into a mixture of benzaldehyde, bromination catalyst and solvent.
6. A process as claimed in claim 4 in which the chlorine is introduced into a mlxture of benzaldehyde, bromination catalyst, bromine and solvent.
7. A process as claimed in claim 6 in which the chlorine is introduced over a period of 1 to 5 hours.
8. A process as claimed in any one of the claims 1, 2 and 4, in which the bromination catalyst is aluminum chloride.
9. A process as claimed in any one of the claims 1, 2 and 4, in which the molar ratio of bromination catalyst to benzaldehyde is from 1:1 to 1.5:1.
10. A process as claimed in any one of the claims 1, 2 and 4, in which the molar ratio of bromine to benzaldehyde is from 0.5:1 to 0.6:1.
11. A process as claimed in any one of the claims 1, 2 and 4, in which the chlorinated hydrocarbon solvent is 1,2-dichloroethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB23771/75A GB1535333A (en) | 1975-06-02 | 1975-06-02 | Process for the preparation of 3-bromo-benzaldehyde |
| GB33076 | 1976-01-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069135A true CA1069135A (en) | 1980-01-01 |
Family
ID=26235853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA251,701A Expired CA1069135A (en) | 1975-06-02 | 1976-05-03 | Process for the preparation of 3-bromobenzaldehyde |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS51143639A (en) |
| BR (1) | BR7603452A (en) |
| CA (1) | CA1069135A (en) |
| CH (1) | CH620188A5 (en) |
| DD (1) | DD124377A5 (en) |
| DE (1) | DE2624410A1 (en) |
| DK (1) | DK238776A (en) |
| FR (1) | FR2313339A1 (en) |
| HU (1) | HU174975B (en) |
| IE (1) | IE42828B1 (en) |
| IL (1) | IL49688A (en) |
| IT (1) | IT1060880B (en) |
| LU (1) | LU75056A1 (en) |
| NL (1) | NL7605829A (en) |
| SU (1) | SU680641A3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3136561A1 (en) * | 1981-09-15 | 1983-03-31 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING PARA-SUBSTITUTED 3-BOMBENZALDEHYDES |
| US4585898A (en) * | 1984-12-18 | 1986-04-29 | Hardwicke Chemical Company | Preparation of substituted benzaldehydes |
-
1976
- 1976-05-03 CA CA251,701A patent/CA1069135A/en not_active Expired
- 1976-05-31 HU HU76SE1836A patent/HU174975B/en unknown
- 1976-05-31 FR FR7616353A patent/FR2313339A1/en active Granted
- 1976-05-31 DD DD193100A patent/DD124377A5/xx unknown
- 1976-05-31 IL IL49688A patent/IL49688A/en unknown
- 1976-05-31 CH CH680876A patent/CH620188A5/en not_active IP Right Cessation
- 1976-05-31 IT IT23799/76A patent/IT1060880B/en active
- 1976-05-31 IE IE1152/76A patent/IE42828B1/en unknown
- 1976-05-31 JP JP51062450A patent/JPS51143639A/en active Pending
- 1976-05-31 DE DE19762624410 patent/DE2624410A1/en not_active Withdrawn
- 1976-05-31 SU SU762363456A patent/SU680641A3/en active
- 1976-05-31 DK DK238776A patent/DK238776A/en not_active Application Discontinuation
- 1976-05-31 NL NL7605829A patent/NL7605829A/en not_active Application Discontinuation
- 1976-05-31 LU LU75056A patent/LU75056A1/xx unknown
- 1976-05-31 BR BR3452/76A patent/BR7603452A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51143639A (en) | 1976-12-10 |
| IL49688A (en) | 1978-12-17 |
| DE2624410A1 (en) | 1976-12-16 |
| AU1444576A (en) | 1977-12-08 |
| IT1060880B (en) | 1982-09-30 |
| IE42828B1 (en) | 1980-10-22 |
| BR7603452A (en) | 1977-01-04 |
| NL7605829A (en) | 1976-12-06 |
| DK238776A (en) | 1976-12-03 |
| CH620188A5 (en) | 1980-11-14 |
| IE42828L (en) | 1976-12-02 |
| FR2313339A1 (en) | 1976-12-31 |
| SU680641A3 (en) | 1979-08-15 |
| HU174975B (en) | 1980-04-28 |
| LU75056A1 (en) | 1977-02-15 |
| DD124377A5 (en) | 1977-02-16 |
| FR2313339B1 (en) | 1978-11-17 |
| IL49688A0 (en) | 1976-07-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |