GB1572684A – Process for preparation of 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones
– Google Patents
GB1572684A – Process for preparation of 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones
– Google Patents
Process for preparation of 1-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones
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Publication number
GB1572684A
GB1572684A
GB12016/78A
GB1201678A
GB1572684A
GB 1572684 A
GB1572684 A
GB 1572684A
GB 12016/78 A
GB12016/78 A
GB 12016/78A
GB 1201678 A
GB1201678 A
GB 1201678A
GB 1572684 A
GB1572684 A
GB 1572684A
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GB
United Kingdom
Prior art keywords
process according
reaction
phenoxy
solvent
acid
Prior art date
1977-03-29
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
GB12016/78A
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.)
1977-03-29
Filing date
1978-03-28
Publication date
1980-07-30
1978-03-28
Application filed by Bayer AG
filed
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Bayer AG
1980-07-30
Publication of GB1572684A
publication
Critical
patent/GB1572684A/en
Status
Expired
legal-status
Critical
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Classifications
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07D—HETEROCYCLIC COMPOUNDS
C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Description
PATENT SPECIFICATION ( 11) 1572 684
0 ( 21) Application No 12016/78 ( 22) Filed 28 March 1978 ( 31) Convention Application No 2 713 777 ( 19) i ( 32) Filed 29 March 1977 in,.
( 33) Fed Rep of Germany (DE) n ( 44) Complete Specification published 30 July 1980 ( 51) INT CL 3 C 07 D 233/54; AO 1 N 43/54, 43/66, C 07 D 249/08 ( 52) Index at acceptance C 2 C 1410 1450 215 220 221 225 226 22 Y 246 250 252 25 Y Y 311 313 314 315 31 Y 332 338 351 355 35 Y 364 36 Y 388 500 50 Y 621 624 625 634 655 661 662 697 699 805 FJ MM UL ( 72) Inventors HERMANN AROLD, HANS-LUDWIG ELBE, ECKART KRANZ, WOLFGANG KRAMER, JORG STETTER, CLAUS STOLZER, RUDOLF THOMAS ( 54) PROCESS FOR THE PREPARATION OF 1-AZOLYL-3,3DIMETHYL 1-PHENOXY-BUTAN-2-ONES ( 71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Germany, of Leverkusen, Federal Republic of 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: 5
The present invention relates to an unobvious process for the preparation of certain known fungicidal 1 azolyl 3,3 dimethyl 1 phenoxy butan 2 ones.
It has already been disclosed that 1 azolyl 3,3 dimethyl 1 phenoxy butan2 ones are obtained when chloropinacolone is heated under reflux in a 1st stage for several hours with phenols in the presence of an acid acceptor in ketones, for example 10 acetone, as solvents, the resulting 3,3 dimethyl 1 phenoxy butan 2 ones are halogenated in the customary manner in a 2nd stage in the presence of a solvent which is inert towards halogenating agents, such, as, in particular, chlorinated hydrocarbons, for example carbon tetrachloride, and finally the 1 (chloro(bromo) 3,3 dimethyl1 phenoxy butan 2 ones thereby formed are reacted in a 3rd stage with azoles 15 in the presence of polar solvents, such as, in particular, ketones, for example acetone, and in the presence of an acid acceptor at temperatures between 20 and 120 C (see German Offenlegungsschriften (German Published Specifications) 2,105,490,
2,201,063 and 2,401,715).
However, this aforesaid process has a number of disadvantages Thus, the 3, 3 20 dimethyl-l-phenoxy-butan-2-ones obtained in the first stage and the 1halogeno-3,3dimethyl-l-phenoxy-butan-2-ones obtained in the second stage must be isolated in each case, since the following reaction proceeds in an optimum manner only in another solvent, whereby a multi-stage process results.
The end product can be isolated and purified only after changing the solvent 25 again, and by means of various successive washing operations which cause heavy pollution of the effluent.
Using various solvents gives rise to an increased expenditure of time, with respect to the working up, and thus higher production costs These are also considerably increased by very long reaction times Thus, this process in its entirety is very un 30 economical Added to this are the frequently unsatisfactory yields.
Furthermore, it has been disclosed that 3,3 dimethyl 1 phenoxy 1 ( 1,2,4triazol 1 yl) butan 2 ones are also obtained when a dihalogenopinacolone is reacted with 1,2,4-triazole and with phenols in the presence of an acidbinding agent and a diluent at temperatures between O and 150 C (see German Offenlegunbsschrift 35 {German Published Specification) 2,406,665).
This prior art process has the disadvantage that competing reactions lead to a greater formation of by-products which considerably lower the yield (at most about %) and make a troublesome and time-consuming working up necessary.
The present invention now provides a process for the preparation of a 1azolyl 40 3,3-dimethyl-1-phenoxy-butan-2-one of the general formula 1.572,684 Yn I CH-CO-C(CH 3)I (I) rri N, in which X represents a nitrogen atom or the CH group, n represents 0, 1, 2, 3 or 4, and Y represents halogen, phenyl, phenoxy, nitro, alkyl, alkoxy or cycloalkyl, the Y’s 5 being selected independently of one another when N is 2 or more, in which 1-chloro-3,3-dimethylbutan-2-one (chloropinacolone), of the formula Cl I-CH 2-CO-C(CH,), (II) is reacted with a phenol of the formula yO,(I)10 À (Ill) Yn in which Y and N have the meanings stated above, in the presence of an optionally nitro-substituted aromatic hydrocarbon or chlorinated aliphatic or aromatic hydrocarbon as a solvent, and in the presence of an acid acceptor, at a temperature of from 60 to 150 C, the ether-ketone formed of the general formula 15 0 CH e-CO -C (CH 3)3 (V Y’in which Y and N have the meanings stated above, is reacted, without isolation, with a halogenating agent in the presence of the same solvent at a temperature of from 20 to 60 C, and finally the halogenoether-ketone 20 thereby formed of the general formula 0 H c H-CO C(CH>)3 (V) Hat Yn H LL in which Y and N have the meanings stated above and Hal represents halogen, aspecially chlorine or bromine, 25 is reacted, also without isolation, with an azole of the general formula H N 1 J (VI) in which X has the meaning stated above, in the presence of the same solvent and in the presence of an acid acceptor at a 30 temperature of from 20 to 120 C.
It is to be described as decidedly surprisingly that the 1 azolyl 3,3 dimethyl1 phenoxy butan 2 ones of the formula (I) can be formed in high yield and purity under the conditions of the process according to the invention, since in the light of the state of the art it had to be expected that it would be possible to arrive 35 3 1,572,684 3 at these compounds only when the solvent is changed four times, especially since it is generally known that nucleophilic substitutions of,-halogenoketmnes proceed particularly well in polar organic solvents, such as ketones, for example acetone, or amides, for example dimethylformamide, or nitriles, for example acetonitrile The successful use of, in particular, an aromatic or chlorinated aliphatic or aromatic hydrocarbon 5 as the solvent for all the indivdual reactions is all the more surprising.
The process according to the invention has a number of advantages Thus, it is a true “one pot process”, in which neither are the intermediate products isolated, nor is the solvent changed.
Reaction times and working-up times which are shortened by more than half, 10 recovery of only one solvent, small amounts of effluent and, additionally, a low salt load, and high yields of 94 % and over, associated with high purity can make the process according to the invention a very economical one.
If chloropinacolone and 4-chlorophenol are used as starting materials, sulphuryl chloride is used as the halogenating agent, 1,2,4-triazole is used as the azole and 15 toluene is used as the solvent, the course of the reaction can be represented by the following equation:
CL-C Hz CO-C(CH 3), + C c, Toluene -HCL CL-Kag O-C He -CO (ct C 3)3 + _ 2 Cj 2 -HCA -Cl Ct-
