CA1048540A - 4-chloro-5-oxo-hexanoic acid nitrile, 6-chloro-5-oxo-hexanoic acid nitrile and process for their manufacture - Google Patents
4-chloro-5-oxo-hexanoic acid nitrile, 6-chloro-5-oxo-hexanoic acid nitrile and process for their manufactureInfo
- Publication number
- CA1048540A CA1048540A CA@@A CA227256A CA1048540A CA 1048540 A CA1048540 A CA 1048540A CA 227256 A CA227256 A CA 227256A CA 1048540 A CA1048540 A CA 1048540A
- Authority
- CA
- Canada
- Prior art keywords
- oxo
- hexanoic acid
- chloro
- acid nitrile
- preparing
- 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
- C07C255/00—Carboxylic acid nitriles
Abstract
4-CHLORO-5-OXO-HEXANOIC ACID NITRILE, AND PROCESS FOR THEIR MANUFACTURE
Abstract of the disclosure:
The compounds 4-chloro-5-oxo-hexanoic acid nitrile and 6-chloro-5-oxo-hexanoic acid nitrile are prepared by chlori-nating 5-oxo-hexanoic acid nitrile in an aqueous 20 to 40%
solution at temperatures of from 25 to 55°C, separating the precipitating oily second phase and submitting it to distil-lation. Said compounds are valuable starting products for preparing ?- or .epsilon. -amino acids and important synthesis pro-ducts for preparing heterocyclic compounds.
Abstract of the disclosure:
The compounds 4-chloro-5-oxo-hexanoic acid nitrile and 6-chloro-5-oxo-hexanoic acid nitrile are prepared by chlori-nating 5-oxo-hexanoic acid nitrile in an aqueous 20 to 40%
solution at temperatures of from 25 to 55°C, separating the precipitating oily second phase and submitting it to distil-lation. Said compounds are valuable starting products for preparing ?- or .epsilon. -amino acids and important synthesis pro-ducts for preparing heterocyclic compounds.
Description
15~48S~O
The pre~ent invention relates to 4-chloro-5-oxo-he~anoic acid nitrile of the ~ormula CH3 - C - CH - CH~ - CHz - CN
Il I ' 0 Cl and 6-chloro-5-oxo-hexanoic acid nitrile of the formula .. . I I .
Cl 0 which have not yet been described in literature.
The present invention further relateo to a process for preparing a mixture of 4-chloro-5-oxo-hexanoic acid nitrile and 6-chloro-5-oxo-hexanoic acid nitrile, which comprises chlorinating 5-oxo-hexanoic acid nitrile in a~ aqueous 20 to 4~ solution at temperaturesof from 25 to 55C.
- The hydrogen chloride liberated in the chlorination is absorbed by water. It is however surprising that the nitrile ; group is not hydrolyzed in the process according to the in-~ention, although such a reaction had to be expected in the Z0 aqueous medium containing hydrochloric acid.
~he trifunctional compounds 4-chloro- and 6-chloro-5-oxo-hexanoic acid nitrile accessible by the present invention are valuable starting products for preparing ~ - or -amino acids and~being ~ -chloroketonestmoreover important synthesis com-ponents for preparing heterocyclic compounds.
The following method has proved especia1ly successful for the chlorination process according to the inventions The starting phase of the chlorination i~ preferably 29 effected at temperatures of from 25 to 40C. When the reac-
The pre~ent invention relates to 4-chloro-5-oxo-he~anoic acid nitrile of the ~ormula CH3 - C - CH - CH~ - CHz - CN
Il I ' 0 Cl and 6-chloro-5-oxo-hexanoic acid nitrile of the formula .. . I I .
Cl 0 which have not yet been described in literature.
The present invention further relateo to a process for preparing a mixture of 4-chloro-5-oxo-hexanoic acid nitrile and 6-chloro-5-oxo-hexanoic acid nitrile, which comprises chlorinating 5-oxo-hexanoic acid nitrile in a~ aqueous 20 to 4~ solution at temperaturesof from 25 to 55C.
- The hydrogen chloride liberated in the chlorination is absorbed by water. It is however surprising that the nitrile ; group is not hydrolyzed in the process according to the in-~ention, although such a reaction had to be expected in the Z0 aqueous medium containing hydrochloric acid.
~he trifunctional compounds 4-chloro- and 6-chloro-5-oxo-hexanoic acid nitrile accessible by the present invention are valuable starting products for preparing ~ - or -amino acids and~being ~ -chloroketonestmoreover important synthesis com-ponents for preparing heterocyclic compounds.
The following method has proved especia1ly successful for the chlorination process according to the inventions The starting phase of the chlorination i~ preferably 29 effected at temperatures of from 25 to 40C. When the reac-
- 2 -HOE 7 4/E` 13 2 . .
tion is in full course and the originally green-yellow colored solution has decolored, chlorination i8 continued at temperatures of from 40 to 55C, preferably of from 40 to 45C. Exterior cooling is generally recommended for main-taining this temperature level. The chlorine quantity reac-~ing in this main reaction phase is about 2 to 3 times the chlorine quantity reacting ~n the starting phase of the chlori-nation. The terminal phase of the chlorination is indicated by a diminution of the chlorine absDrption and by the yellow coloring of the reaction solution to be observed anew. The opacity of the solution wh$ch already occurs in the starting phase indicates the precipitation of the water insoluble chlorination products. Further chlorination of theses products i9 prevented by said precipitation.
The two chloro-keto-nitriles prepared by the process according to the invention may be isolated in quite simple manner. When terminating the chlorination the precipitating organic bottom phase is separated, washed with water and distilled without intermediate drying. Both components may be readily separated owing to the fact that there is an inter-val of 30 C between their boiling points.
The following example illustrate the invention.
E X A M P L_E s A solution of 333 g (3 moles) of 5 oxo-hexanoic acid nitrile in 1332 ml of water was introduced into a 2 liter flask and gaseous chlorine was added while stirring at a tem-perature of from 40 to 42 C, -until the stoichiometrically required chlorine quantity had been absorbed.
29 After terminating the chlorine absorption stirring was -- 3 ~
- : . ~
` HOE 74/F 1~2 - 1~)4~3540 continued for 1 hour, the organic phase wa~ separated and wa~hed twice with 400 ml of water each time.
m e reaction product was then distilled over a vacuum . ~acket column(length 100 cm, diameter 25 mm)-charged with ; 5 Raschig rings (di~meter 4 mm) and a quantity of 205 g of 4-chloro-5-o~o-hexanoic acid nitrile corresponding to a yield of 47.3% of the theory wa~ isolated at a boiling point of 90C (1 mm Hg) and a quantity of 95 g of 6-chloro-5-oxo-. hexanoic acid nitrile corresponding to a yield Or 21.5% of tO the theory at a boiling point of 118C (1 ~ m Hg) .
Both new compounds are cle~r liquid~ Or a density of 1.i5.
,.. . .
,. . .
, . . .
.~ . . -- .
,~, . .
. ~ . . .
. ~
, . .
i 1, . . .
,, . .
~ .
'I - .
1 .
., .
" ~ .
,. . .
.~
i _ 4 _ .' - . , . :
.
:' ' .: . ' : - ' ' . ' ~ ' ' ' : :': . .
tion is in full course and the originally green-yellow colored solution has decolored, chlorination i8 continued at temperatures of from 40 to 55C, preferably of from 40 to 45C. Exterior cooling is generally recommended for main-taining this temperature level. The chlorine quantity reac-~ing in this main reaction phase is about 2 to 3 times the chlorine quantity reacting ~n the starting phase of the chlori-nation. The terminal phase of the chlorination is indicated by a diminution of the chlorine absDrption and by the yellow coloring of the reaction solution to be observed anew. The opacity of the solution wh$ch already occurs in the starting phase indicates the precipitation of the water insoluble chlorination products. Further chlorination of theses products i9 prevented by said precipitation.
The two chloro-keto-nitriles prepared by the process according to the invention may be isolated in quite simple manner. When terminating the chlorination the precipitating organic bottom phase is separated, washed with water and distilled without intermediate drying. Both components may be readily separated owing to the fact that there is an inter-val of 30 C between their boiling points.
The following example illustrate the invention.
E X A M P L_E s A solution of 333 g (3 moles) of 5 oxo-hexanoic acid nitrile in 1332 ml of water was introduced into a 2 liter flask and gaseous chlorine was added while stirring at a tem-perature of from 40 to 42 C, -until the stoichiometrically required chlorine quantity had been absorbed.
29 After terminating the chlorine absorption stirring was -- 3 ~
- : . ~
` HOE 74/F 1~2 - 1~)4~3540 continued for 1 hour, the organic phase wa~ separated and wa~hed twice with 400 ml of water each time.
m e reaction product was then distilled over a vacuum . ~acket column(length 100 cm, diameter 25 mm)-charged with ; 5 Raschig rings (di~meter 4 mm) and a quantity of 205 g of 4-chloro-5-o~o-hexanoic acid nitrile corresponding to a yield of 47.3% of the theory wa~ isolated at a boiling point of 90C (1 mm Hg) and a quantity of 95 g of 6-chloro-5-oxo-. hexanoic acid nitrile corresponding to a yield Or 21.5% of tO the theory at a boiling point of 118C (1 ~ m Hg) .
Both new compounds are cle~r liquid~ Or a density of 1.i5.
,.. . .
,. . .
, . . .
.~ . . -- .
,~, . .
. ~ . . .
. ~
, . .
i 1, . . .
,, . .
~ .
'I - .
1 .
., .
" ~ .
,. . .
.~
i _ 4 _ .' - . , . :
.
:' ' .: . ' : - ' ' . ' ~ ' ' ' : :': . .
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. 5-Oxo-hexanoic acid nitriles selected from the group consisting of 4-chloro-5-oxo-hexanoic acid nitrile of the form-ula and 6-chloro-5-oxo-hexanoic acid nitrile of the formula
2. 4-Chloro-5-oxo-hexanoic acid nitrile of the formula
3. 6-Chloro-5-oxo-hexanoic acid nitrile of the formula
4. A process for preparing the compounds claimed in claim 1, in which 5-oxo-hexanoic acid nitrile is reacted with chlorine in an aqueous 20 to 40% solution of the acid nitrile at a temperature of from 25 to 55°C.
5. A process as claimed in claim 4 for preparing 4-chloro-5-oxo-hexanoic acid nitrile, in which the oily second phase precipitated during the reaction is separated and distilled to isolate 4-chloro-5-oxo-hexanoic acid.
6. A process as claimed in claim 4 for preparing 6-chloro-5-oxo-hexanoic acid nitrile, in which the oily second phase precipitated during the reaction is separated and distil-led to isolate 6-chloro-5-oxo-hexanoic acid nitrile.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19742423316 DE2423316C2 (en) | 1974-05-14 | 1974-05-14 | Process for the production of 4-chloro-5-oxo-hexanoic acid nitrile and 6-chloro-5-oxo-hexanoic acid nitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048540A true CA1048540A (en) | 1979-02-13 |
Family
ID=5915488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA@@A Expired CA1048540A (en) | 1974-05-14 | 1975-05-13 | 4-chloro-5-oxo-hexanoic acid nitrile, 6-chloro-5-oxo-hexanoic acid nitrile and process for their manufacture |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5934703B2 (en) |
| CA (1) | CA1048540A (en) |
| CH (1) | CH612174A5 (en) |
| DE (1) | DE2423316C2 (en) |
| GB (1) | GB1492103A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7609478A (en) * | 1976-08-26 | 1978-02-28 | Stamicarbon | PROCESS FOR THE PREPARATION OF 4-OXOCAPRONI TRIL. |
| US5106984A (en) * | 1985-12-20 | 1992-04-21 | The Dow Chemical Company | 2-hydrocarbyl-3,6-dichloropyridines and their preparation |
| DE3779756T2 (en) * | 1987-09-09 | 1992-12-10 | Dowelanco | 2-HYDROCARBYL-3,6-DICHLORPYRIDINE AND THEIR PRODUCTION. |
-
1974
- 1974-05-14 DE DE19742423316 patent/DE2423316C2/en not_active Expired
-
1975
- 1975-05-09 CH CH598975A patent/CH612174A5/en not_active IP Right Cessation
- 1975-05-12 GB GB1984275A patent/GB1492103A/en not_active Expired
- 1975-05-12 JP JP5477875A patent/JPS5934703B2/en not_active Expired
- 1975-05-13 CA CA@@A patent/CA1048540A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2423316A1 (en) | 1975-11-27 |
| GB1492103A (en) | 1977-11-16 |
| JPS5934703B2 (en) | 1984-08-24 |
| DE2423316C2 (en) | 1983-01-27 |
| CH612174A5 (en) | 1979-07-13 |
| JPS50154209A (en) | 1975-12-12 |
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