GB1574548A – 1-chloro-3,3-dimethyl-butan-2-one
– Google Patents
GB1574548A – 1-chloro-3,3-dimethyl-butan-2-one
– Google Patents
1-chloro-3,3-dimethyl-butan-2-one
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Publication number
GB1574548A
GB1574548A
GB14135/78A
GB1413578A
GB1574548A
GB 1574548 A
GB1574548 A
GB 1574548A
GB 14135/78 A
GB14135/78 A
GB 14135/78A
GB 1413578 A
GB1413578 A
GB 1413578A
GB 1574548 A
GB1574548 A
GB 1574548A
Authority
GB
United Kingdom
Prior art keywords
pinacoline
process according
reaction
carried out
monochloropinacoline
Prior art date
1977-04-16
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
Application number
GB14135/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
1977-04-16
Filing date
1978-04-11
Publication date
1980-09-10
1978-04-11
Application filed by Bayer AG
filed
Critical
Bayer AG
1980-09-10
Publication of GB1574548A
publication
Critical
patent/GB1574548A/en
Status
Expired
legal-status
Critical
Current
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Classifications
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
Description
PATENT SPECIFICATION
Application No 14135/78 ( 22) Filed 11 April 1978 Convention Application No 2716896 Filed 16 April 1977 in Federal Republic of Germany (DE) Complete Specification published 10 Sept 1980
INT CL 3 C 07 C 49/16 C 07 B 9/00 ( 52) Index at acceptance C 2 C 209 20 Y 313 31 Y 339 351 35538641141341441641 Y 440 625 655 FH UU ( 72) Inventors ECKART KRANZ RUDIGER SCHUBART HERBERT SCHWARZ PETER SIEGLE and HEINRICH STEUDE ( 54) 1 I-CHLORO-3,3-DIMETHYL-BUTAN-2-ONE ( 71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Federal Republic of Germany of Leverkusen, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The invention relates to a process for the preparation of I chloro 3,3 dimethyl butan 2 one (monochloropinacoline).
It is known that monochloropinacoline is obtained when pinacoline is chlorinated in the presence of a solvent, such as, for example, carbon tetrachloride, chloroform or carbon disulphide, at room temperature under UV radiation (J Am Chem Soc 55, 2,509 to 2,512 ( 1933)) However, the yield of 23 ‘ is very low.
Similar processes which are carried out in the presence or in the absence of water or in the presence of catalysts, such as, for example, iron or iodine, or in the presence of buffer substances, such as sodium carbonate, or which are carried out electrolytically lead to no improvement in yield (J Am Chem Soc 55, 2,509 to 2,512 ( 1933)).
The reaction of pinacoline with equivalent amounts of chlorine to give monochloropinacoline without a solvent at 0 C has also been disclosed (C A 53, 5,185 ( 1959)) This process has the disadvantage that the reaction is only incomplete and the yield is low Increasing the temperature to or 40 C leads to increased formation of dichloropinacoline.
Furthermore, it has been disclosed that monochloropinacoline is obtained by gas phase chlorination of pinacoline by passing a dry stream of chlorine into the gas phase of pinacoline and separating the reaction products by fractional distillation (J Org.
Chem 11, 781 to 787 ( 1946)) However, this process has the disadvantage that considerable amounts of by-products, such as 1,1 dichloro 3,3 dimethyl butan 2 one and 1,4 dichloro 3,3 dimethyl butan 2 one, are formed.
In addition, it has been disclosed that the chlorination of pinacoline to give monochloropinacoline can be carried out with seleniumoxy dichloride (J Org Chem.
28, 1,128 ( 1963)) The yield of the reaction is low here also.
A process has been found for the preparation of monochloropinacoline by chlorinating pinacoline in the temperature range of-20 to 160 C in which an excess of pinacoline, which has a temperature of -20 to 70 C, is reacted with chlorine.
The process according to the invention can be illustrated with the aid of the following equation:
0 II 0 CH 3 C C(CH 3)a+CI 2Il Cl-CH 2-C-C(CH 3)3 +HCI An excess of pinacoline is reacted with chlorine by the process according to the invention For reasons of expediency, in general an excess of 1 to 50 mols, preferably of 5 to 20 mols, of pinacoline is employed per mol of chlorine.
The process according to the invention is preferably carried out in a temperature range from 0 to 80 C.
In the process according to the invention, the temperature of the pinacoline fed to the reaction is in the range from -20 to 70 C, preferably from -10 to 20 C.
The process according to the invention ( 21) ( 31) ( 32) ( 33) ( 44) ( 51) ( 11) 1 574 548 2 1 574548 7 can be carried out under reduced, normal or elevated pressure, preferably under normal pressure.
Anhydrous pinacoline can be used for the process according to the invention.
Anhydrous pinacoline can be obtaihed, for example, by subjecting industrial pinacoline to incipient distillation.
In a preferred embodiment of the process according to the invention, the reaction is carried out with water-containing pinacoline In general, it is possible to use pinacoline which contains up to 20 per cent by weight, preferably from 0 01 to 5 per cent by weight, of water.
In a further preferred embodiment of the process according to the invention, the reaction is carried out with the exclusion of light.
In the process according to the invention, gaseous chlorine is passed into the reaction chamber The chlorine can be used without further diluents However, it is also possible to dilute the gaseous chlorine with inert gases, such as nitrogen or argon The proportion of diluent can then be up to 90 %, preferably from 30 to 50 %, of the gas employed.
The process according to the invention is preferably carried out in a reaction apparatus in which the pinacoline has a short residence time and is chlorinated to the extent of only a few per cent by weight and the chlorination mixture formed is removed from the reaction apparatus immediately after the chlorination and further chlorination of the already chlorinated reaction mixture is thus avoided.
It is possible to carry out the process according to the invention either discontinuously or continuously.
An embodiment of the process according to the invention is illustrated with the aid of the drawing:
The pinacoline is fed via ( 1) and, if appropriate, the water is fed via ( 2) into the head ( 3) of a column ( 13) which has an inlet ( 11) in the middle section and an outlet ( 14) in the bottom ( 12) and which is packed or provided with glass trays The pinacoline and, if appropriate, the water, evaporate in the head ( 3) of the column and are passed via feed line ( 4) to the dephlegmator ( 5) and condensed there The condensed, optionally water-containing pinacoline is passed via feed line ( 7) to the cooler ( 9), in which the liquid pinacoline is brought to the temperature at which it is passed into the reactor ( 10) Gaseous chlorine is fed via feed line ( 8) into the reactor ( 10), which can be appropriately warmed or cooled to the desired reaction temperature It is possible to darken the reactor ( 10) The reactor, for example a Venturi tube, is designed so that the reaction product can be led out of the reactor as rapidly as possible after the reaction.
The reaction mixture formed, which essentially contains monochloropinacoline, unreacted pinacoline and hydrogen chloride, is passed through the inlet ( 11) into the middle section of the column ( 13) The reaction mixture formed is separated in the column ( 13) The unreacted pinacoline and the hydrogen chloride are removed via the head ( 3) of the column ( 13); both compounds are passed via feed line ( 4) into the dephlegmator ( 5), in which the hydrogen chloride is separated off via head ( 6), whilst the pinacoline is recycled to the reaction.
The monochloropinacoline formed during the reaction is removed at the bottom ( 12) of the column ( 13) via the outlet ( 14).
It is advantageously possible to prepare monochloropinacoline in high yields on an industrial scale with the aid of the process according to the invention Virtually no byproducts are formed in the process according to the invention By recirculating the pinacoline, virtually no loss of the pinacoline employed occurs.
It is surprising that monochloropinacoline is formed in high yield and purity under the process conditions according to the invention since, with regard to the state of the art, it should have been expected that unsatisfactory amounts of monochloropinacoline and large amounts of byproducts, such as 1,1 dichloropinacoline, 1,4 dichloropinacoline and 4 chloropinacoline, are formed in the chlorination of pinacoline in the liquid phase and without a solvent.
Monochloropinacoline can be used as an intermediate product for the synthesis of known fungicidal and antimicrobial active compounds, such as 1 ( 4 chlorophenoxy) 3,3 dimethyl 1 ( 1,2,4 triazol 1 yl) butan 2 one and 1 ( 4 chlorophenoxy 3,3 dimethyl 1 imadazol 1 yl) butan 2 one (DT-OS (German Published Specification) 2,201,063, DT-OS (German
Published Specification 2,401,715 and DT-
OS (German Published Specification)
2,105,490).
In the Example which follows, monochloropinacoline is prepared in a reaction apparatus such as is represented in the drawing.
EXAMPLE
350 ml of pinacoline per hour, with a water content of 0 1 % by weight, are passed into the head ( 3) of the column of a glass tray column ( 13) ( 13 trays, 50 mm cross section) The water-containing pinacoline evaporates and is condensed in the 1.574548 1,574,548 dephlegmator ( 5), which is cooled with water, and passed via feed line ( 7) to the cooler ( 9), in which it is cooled to -10 C.
The pinacoline is passed from the cooler ( 9) to the reactor ( 10), in which it is reacted, at a flow rate of 1 m/second, with the chlorine fed in via ( 8) The reaction product is introduced at the 10th tray of the column ( 13) and then separated Unreacted pinacoline and the hydrogen chloride formed are removed via the head of the column ( 13) The pinacoline is condensed in the dephlegmator ( 5) and is recycled to the reaction 350 ml/hour of monochloropinacoline (with a monochloropinacoline content of 92 5 %) are removed at the bottom of the column ( 13).
Boiling point= 170 to 175 C.
Claims (9)
WHAT WE CLAIM IS:-
1 A process for the production of monochloropinacoline by the chlorination of pinacoline in a temperature range of-20 to 160 C in which an excess of pinacoline, having a temperature of -20 to 70 C, is reacted with chlorine.
2 A process according to claim 1, in which I to 50 moles of pinacoline are employed per mol of chlorine.
3 A process according to claim 2, in which 5 to 20 mols of pinacoline are employed per mol of chlorine.
4 A process according to any of the foregoing claims, in which the reaction is carried out in the presence of water.
A process according to any of the foregoing claims, in which the reaction is carried out in the presence of up to 20 percent by weight of water in the reacted pinacoline.
6 A process according to claim 5, in which the reaction is carried out in the presence of from 0 01 to 5 parts by weight of water per part by weight of pinacoline.
7 A process according to any of the foregoing claims in which the reaction is carried out with the exclusion of light.
8 A process according to claim 1, when carried out substantially as described in the Example.
9 Monochloropinacoline when produced by the process of any of the foregoing claims.
Chartered Patent Agents, For the Applicants, CARPMAELS & RANSFORD, 43 Bloomsbury Square, London WC 1 A 2 RA.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa 1980 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
GB14135/78A
1977-04-16
1978-04-11
1-chloro-3,3-dimethyl-butan-2-one
Expired
GB1574548A
(en)
Applications Claiming Priority (1)
Application Number
Priority Date
Filing Date
Title
DE2716896A
DE2716896B1
(en)
1977-04-16
1977-04-16
Process for the preparation of 1-chloro-3,3-dimethyl-butan-2-one
Publications (1)
Publication Number
Publication Date
GB1574548A
true
GB1574548A
(en)
1980-09-10
Family
ID=6006440
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
GB14135/78A
Expired
GB1574548A
(en)
1977-04-16
1978-04-11
1-chloro-3,3-dimethyl-butan-2-one
Country Status (16)
Country
Link
US
(1)
US4196150A
(en)
JP
(1)
JPS53130615A
(en)
BE
(1)
BE865972A
(en)
BR
(1)
BR7802320A
(en)
CH
(1)
CH638479A5
(en)
CS
(1)
CS207718B2
(en)
DD
(1)
DD135823A5
(en)
DE
(1)
DE2716896B1
(en)
DK
(1)
DK170798B1
(en)
FR
(1)
FR2387208A1
(en)
GB
(1)
GB1574548A
(en)
HU
(1)
HU174535B
(en)
IL
(1)
IL54499A
(en)
IT
(1)
IT1105006B
(en)
NL
(1)
NL190843C
(en)
SU
(1)
SU799644A3
(en)
Families Citing this family (6)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
DE3049461A1
(en)
*
1980-12-30
1982-09-09
Bayer Ag, 5090 Leverkusen
METHOD FOR PRODUCING MONOCHLORMETHYLKETONES
DE3204788A1
(en)
*
1982-02-11
1983-08-18
Bayer Ag, 5090 Leverkusen
METHOD FOR PRODUCING 5-SUBSTITUTED 1-CHLORINE-3,3-DIMETHYLPENTAN-2-ONES
DE3400829A1
(en)
*
1984-01-12
1985-07-18
Basf Ag, 6700 Ludwigshafen
ALPHA-HALOGEN-PHENOXYALKYLKETONE, PHENOXYALKYLKETONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INTERMEDIATE PRODUCTS FOR THE PRODUCTION OF FUNGICIDES
US4642385A
(en)
*
1985-11-19
1987-02-10
Mobay Corporation
Preparation of monochloropinacolone
CN107686443A
(en)
*
2017-09-27
2018-02-13
南通利奥化工科技有限公司
A kind of production method of chlorine pinacoline
CN112430180A
(en)
*
2020-10-24
2021-03-02
湖北山水化工有限公司
Process system and process for preparing chloropinacolone
Family Cites Families (7)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
DE698778C
(en)
*
1934-11-11
1941-07-10
I G Farbenindustrie Akt Ges
Process for the preparation of organic monochloro or monobromo compounds
US2120392A
(en)
*
1937-12-30
1938-06-14
Goodrich Co B F
Continuous process for the chlorination of ketones
US2235562A
(en)
*
1938-09-01
1941-03-18
Eastman Kodak Co
Method for producing chlorinated ketones
US2243484A
(en)
*
1939-04-28
1941-05-27
Commercial Solvents Corp
Process for the preparation of monohalogenated ketones
DE954694C
(en)
*
1952-12-28
1956-12-20
Basf Ag
Process for the chlorination of insoluble or only slightly water-soluble ketones or secondary alcohols of the aliphatic or cycloaliphatic series
US3397240A
(en)
*
1962-07-24
1968-08-13
Merck & Co Inc
Process for the monohalogenation of acetone
JPS53137908A
(en)
*
1977-05-10
1978-12-01
Shionogi & Co Ltd
Syntheses of monochloropinacolone and cyanopinacolone
1977
1977-04-16
DE
DE2716896A
patent/DE2716896B1/en
active
Granted
1978
1978-03-29
US
US05/891,561
patent/US4196150A/en
not_active
Expired – Lifetime
1978-04-11
GB
GB14135/78A
patent/GB1574548A/en
not_active
Expired
1978-04-12
CH
CH392778A
patent/CH638479A5/en
not_active
IP Right Cessation
1978-04-12
HU
HU78BA3647A
patent/HU174535B/en
unknown
1978-04-13
NL
NL7803950A
patent/NL190843C/en
not_active
IP Right Cessation
1978-04-13
IL
IL54499A
patent/IL54499A/en
unknown
1978-04-14
DD
DD78204800A
patent/DD135823A5/en
not_active
IP Right Cessation
1978-04-14
JP
JP4338678A
patent/JPS53130615A/en
active
Granted
1978-04-14
FR
FR7811087A
patent/FR2387208A1/en
active
Granted
1978-04-14
BR
BR7802320A
patent/BR7802320A/en
unknown
1978-04-14
CS
CS782446A
patent/CS207718B2/en
unknown
1978-04-14
DK
DK164878A
patent/DK170798B1/en
not_active
IP Right Cessation
1978-04-14
IT
IT48903/78A
patent/IT1105006B/en
active
1978-04-14
BE
BE2056872A
patent/BE865972A/en
not_active
IP Right Cessation
1978-04-14
SU
SU782602549A
patent/SU799644A3/en
active
Also Published As
Publication number
Publication date
NL7803950A
(en)
1978-10-18
JPS53130615A
(en)
1978-11-14
IL54499A
(en)
1980-10-26
DD135823A5
(en)
1979-05-30
SU799644A3
(en)
1981-01-23
IL54499A0
(en)
1978-07-31
BR7802320A
(en)
1978-12-19
US4196150A
(en)
1980-04-01
CS207718B2
(en)
1981-08-31
JPS6126769B2
(en)
1986-06-21
CH638479A5
(en)
1983-09-30
HU174535B
(en)
1980-02-28
BE865972A
(en)
1978-10-16
DE2716896C2
(en)
1979-06-28
IT1105006B
(en)
1985-10-28
DK170798B1
(en)
1996-01-22
NL190843C
(en)
1994-09-16
FR2387208A1
(en)
1978-11-10
DE2716896B1
(en)
1978-11-02
FR2387208B1
(en)
1984-09-14
DK164878A
(en)
1978-10-17
IT7848903D0
(en)
1978-04-14
NL190843B
(en)
1994-04-18
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Legal Events
Date
Code
Title
Description
1980-11-26
PS
Patent sealed [section 19, patents act 1949]
1998-05-06
PE20
Patent expired after termination of 20 years
Effective date:
19980410
