TW390873B - A process for preparing 2-(substituted benzoyl)-1,3-cyclohexanedione compounds - Google Patents

Description

A7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs --- _B7 _ V. Description of the invention (1) The invention relates to the preparation of 2- (substituted phenylfluorenyl) -1,3-cyclohexanedione compounds . 2- (substituted phenylfluorenyl) -1,3-cyclohexanedione is known as a herbicide, from, for example, U.S. Patent No. 4,78.0,127, U.S. Patent No. 4,80,146, and U.S. Patent No. No. 4,946,981, U.S. Patent No. 5,006,158, 0940S988 and WO 94 (M524. One method of preparing these compounds is by rearrangement of enol esters. This method is disclosed in U.S. Patent No. 4,780,127 and U.S. Patent No. No. 4,695,673. This method provides a method for obtaining such desired compounds, but when an alkali metal carbonate is used as a base, it usually uses an organic base such as triethylamine or a polar aprotic solvent. Organic bases and polar non The use of protonic springs has problems in the industrial specifications due to the need for a final recovery of such materials. It has been surprisingly found that if a critical amount of water is added to the reaction medium, a non-polar A solvent according to the present invention provides a method for preparing a compound of formula (I), wherein R 1, R 2, R 3, r 4, and R 5 are each independently hydrogen or alkyl; R 7 is halogen, cyano, NO 2, ( ^ "Burning; Cu Alkyl, C ^ -4 alkyloxy or RaS where Ra is Ci_4 ^ yl 'r8' r9 and Rio are independently nitrogen, halogen, alkyl, Ci_4alkoxy, Ci_4alkyl, 0_4_alkoxy Group 'CN' N02, phenoxy or substituted phenoxy; RbS (0) n Om where m is 0 or i, n is 0, and alkyl, haloalkyl, phenyl or benzyl, NHCORc where Rc ^ Cl_4 alkyl, ^^^ where Rd and Re are independently hydrogen or Ci-4 alkyl; Rfc (〇) _ where Rf is hydrogen, Cl_4 alkyl, Ci, 4-haloalkyl or fluorene 1-4 alkoxy; spjNRgRh Of which—4 paper sizes are in accordance with Chinese National Standard (CNS) A4 specifications (210x297) (Read the notes on the back first and then fill out this page) ¾ ------ h-order --- r. ^ ------------ A7 B7 V. Description of the invention (2

Rg and Rh are independently hydrogen or. p GQ Q alkyl; or any divalent carbon atom in R8, R9, and Rio—to form a group containing up to three selected from 0, (# first read the notes on the back and then fill out this page) = or although atomic 5 or 6-membered heterocyclic ring and it is optionally substituted with Cl.4 alkyl, i_4haloalkyl'Cb4alkoxy, = noCi_4alkyl or halogen; the method includes replacing a compound of formula (") (wherein R1 , R2, 1r3, R4, R5, R6 9 R7? R8?. And R as defined in relation to formula (I)) rearrangement, ^ in non-polar tinctures, in the source of cyanide, test or test The earth metal carbonic acid phase I is a 4-phase catalyst and is reacted with a compound of formula (JJ) in the presence of 1 to 6 moles of water. / The term "alkyl" as used herein refers to a straight or branched chain. The term "alkyl" refers to an alkyl group substituted with at least one self prime. Similarly, the term "haloalkoxy" refers to an alkyloxy group substituted with at least one prime. The term used herein " Halogen " means fluorine, chlorine, bromine and iodine. Suitable optional substituents R for phenoxy R8, feet 9 and feet 10 include halogens such as fluorine and chlorine, and C14li alkyl. I) A preferred group of compounds are those compounds, wherein Ri, R2, 'R4', R3 and r6 are independently hydrogen or Ci_6 alkyl; R7 is halogen, cyano-N02 'alkyl; Ci_4 haloalkyl, Ci4 Alkoxy or RaS is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. • China 1 ^ is Ci.4 alkyl, R8, R9 * R10 are independently hydrogen, halogen, c4 alkyl, Ci_4 alkoxy, Cl_4 From alkyl, Cl_4 alkylalkoxy, CN, N02, phenoxy or substituted phenoxy; RbS (0) n 0m where or 1, n is 0, 1 or 2 and Rb is Ci-4 alkyl , Haloalkyl, phenyl or benzyl, NHCORc where rc is Ci_4 alkyl, NRdRe where Rd and Re are independently hydrogen or Cb4 alkyl; RfC (O)-where Rf is hydrogen, Ci_4 alkyl, -5- This Paper scale suitable for China Home Standard (CNS) A4 specification (210X297 mm) V. Description of the invention (3 Printed by A7 B7 1.4 haloalkyl or Ci_4 alkoxy group of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs; or S02NRgRh where Rg and Rh are independently hydrogen or Ci_4 alkyl. Preferably, R1, R2, R3, R4, R5 * R6 are independently hydrogen or & 4 alkyl. More preferably, A1, R2 ', R3 and R6 are hydrogen, and R3 and R4 are independently hydrogen or methyl. R7 is preferably halogen or N02. R8 is preferably hydrogen. R9 is preferably hydrogen or (^ _4 alkoxy, especially ethoxy. Most preferably, R9 is chlorine. More preferably, R10 is RbS (0) n 0m group, whose * Rb is as defined above. More preferably m is zero, η is 2 and Rb is CH3 or C2H5. Most preferably, R1G is CH3S02 attached to the 4-position of benzamidine group. The term "source of cyanide" means, under rearrangement conditions, one or more substances that consist of or generate hydrogen cyanide and / or cyanide anion. Preferred cyanide . The source of the compound is alkali metal cyanide, such as steel cyanide and dry; methyl alkyl ketone cyanohydrin having i_4 carbon atoms in the alkyl group, such as acetone or fluorenyl isobutyl ketone cyanohydrin; Formaldehyde cyanohydrin; CyC5 aliphatic aldehyde cyanohydrin, such as acetaldehyde cyanohydrin, propionaldehyde cyanohydrin, etc .; cyclohexanone cyanohydrin; triethylamine_hcn complex; tetrabutylammonium bromide / CN-mixture; lactonitrile ; Lower alkyl silane cyanides, especially di- and tri- (lower alkyl) silane cyanides such as dimethyl and trifluorenyl cyanide; ferrocyanine; and hydrocyanic acid itself. More preferably, the source of the cyanide is metal cyanide, and the most preferred is sodium cyanide. The amount of cyanide source used is up to about 50 mole percent based on the enol ester. It can be used in a small scale, such as about i mole percentage = volume 6 This paper size is applicable to China National Standard (CNS) A4 specifications (21 × 297 mm) (Please read the precautions on the back before filling out this page )

V. Description of the invention (4) ^ An acceptable reaction material is caused in the contract. Large-scale reactions have caused this page to be read before reading the notes of interest. A slightly higher amount of catalyst * yielded more reproducible results, while 3, about 1-10 mole% of the cyanide source was the better. This method is carried out with an excessive amount of alkali or alkaline earth metal carbonate relative to the alcohol-forming compound of formula (11), and sodium carbonate is preferred. Theta test or soil metal salt is used in an amount of about 1 to about 4 moles per mole of enol S &, preferably about 2 moles per mole. Isothermal dissolution is used in this method, depending on the nature of the reactant. The preferred solvent for this reaction is toluene. Depending on the reactants or products, other mixtures used include aromatic hydrocarbons such as dibenzobenzene, anisin, and umbelliferol, or amines, such as hexamidine, or ring filaments, such as cyclohexane. The choice of phase transfer catalyst for t can be determined by well-known procedures known to skilled chemists. Known phase transfer catalysts include tetraalkylammonium sulfide and phosphonium salts. Preferred catalysts are autoalkylated tetraalkylammonium, especially tetrabutylammonium bromide. Phase transfer catalysts are usually used at 1-10 mole%. Water is preferably used at 2-6 moles, especially 4 moles per mole of enol ester. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, based on the nature of the reactants and the source of cyanide, rearrangement can be performed at a temperature of 0 ° C, up to about 10 (rc. Better, the maximum temperature Is about 80 ° C. Optimally, the temperature is from about 20. (: to about 70X :. In some cases, such as when there may be problems with excessive by-product formation (for example, when using o-nitrate Phenylbenzyl halide), the temperature should be kept at about 40 ° C. The method can be carried out using the enol ester as the starting material, or in-situ formation of associated ester, such as the reaction formula (III) Compounds, among which R1, R2, r3, r4 are applicable to China National Standard (CNS) A4 specification (210X297 mm). This paper is produced by the Central Government Bureau of the Ministry of Economic Affairs for consumer cooperation, and is printed by 1M873 B7. 5. Description of the invention ( 5), R and R6 are as defined in relation to formula (I), compounds of formula (IV), Lizhong 117, R8, R4R10 are as defined in relation to formula ⑴, and Z is a quotient, preferably Chlorine. When enol esters are used as starting materials, they can be any of a number of known methods. The preparation includes a compound of formula (m) and a compound of formula (IV) for donkeys. The preparation of a compound of formula (I) according to the present invention can be advantageously carried out starting from compounds of formula (π) and (jv), and can It is carried out in the presence or absence of the intermediate product, fetoester (II). When it is carried out in two steps, the compound of formula (III) and the compound of formula (IV) are reacted in the presence of carbonates. The enol ester is separated from the resulting product mixture by known techniques, such as washing the resulting solution with acid and alkali, washing with a saturated sodium chloride solution, and drying. When a different solvent is used for the second step- This technique is advantageous when rearrangement of the femin ester to the compound of formula (1) is preferred. The dried enol ester can be mixed with a common solvent such as acetonitrile, i, 2-dichloroethane, or Toluene is contacted with an appropriate amount of cyanide source, the pre-catalyst phase, sodium carbonate and water, and then heated to a certain temperature to produce the final product. In a better selective method, the enol ester can be retained at Product, and the first campaign can be achieved by increasing the source of cyanide Water and, if necessary, an additional hindrance 1 are carried out using a compatible solvent) to produce a compound of formula (1). Similar yields can be obtained in the presence of or, alcohol esters. The compound of formula (I) may be a salt thereof. The form is obtained from the reaction. The desired compound of formula (I) can be obtained by acidification and extraction with a suitable solvent. The method of the present invention is illustrated by the following examples. --- ί —— Pack 1 ____ (Please read the notes on the back before filling this page) --- Order 丨 丨-^ ---- Ice ----; --Ί. •! II-Economy Ministry of Standards and Technology Bureau Employee Consumption Cooperation Du printed 390873 at B7 V. Description of the Invention (6) Example 1 Put toluene (2 2_g) into a 250-neck four-necked flame drying round bottom rinsed with n2_ Burn and close to Drierite protection tube and oil bubbler. Charge 1,3-cyclohexanedione (5.0 g) and sodium decomposing powder (12.0 g) to produce a red mud. The mass was heated to 5 5 -5 7 Torr and held for 20 minutes. 2-Chloro-4- (fluorenylsulfonyl) benzyl chloride (110 g) was added to toluene: (25 g) and combined. -----------Heating To obtain a complete solution. At 55_57. (:, Via a hot dropping funnel ,. This solution was added dropwise to the mass over 20 minutes to produce a pale yellow slurry. The mass was maintained at 55-57 ° C at 2: K. Add cyanide Sodium chloride (0.103 g), tetra-n-butylammonium (0 "3 g) and water (Mg) in bromide, and the reaction was kept at this temperature for another three hours. The reaction formed on the bottom of the bottle The solid (which cannot be stirred) was sieved, and the paste and clarified liquid were analyzed. The desired compound of formula (1) as a sodium salt was prepared in a yield of 81.6%. The above steps were repeated but the water was omitted, and all the The desired product. ”Using 8 moles of water and enol enol ester for the second time. Repeat the steps of Example [, and the yield of the desired product is less than 1. '(谙 Please read the precautions on the back before filling in this page)

Sheet of paper

390873 B; V. Description of the invention Chemical formula .. (in the description)

Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs

This paper size applies to Chinese national standards. (CNS) A4 size (210X297 mm) ml * mm —.Ha nfl ^ — m Βι ^ ϋ mf? _ Flm ml nm n ^ l- vm- * J n > il nn a ^ K— fm ^ — > ^ 1 0¾-一 vu · (Please read the precautions on the back before filling in this page)

Claims (1)

Application for Public Interest _873 Amendment of the Garden (February 88) Article A8 B8 C8. Scope of patent application mi -1¾] 1. A method for preparing a compound of formula (I): ο (Please read the notes on the reverse side before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ... R1, R2, R5 & R6 are ammonia; r3 & r4 is independently 氲 or methyl; R7 is 卣Element, N02, di-Cwl group; Cm is alkyl or cr.4 ^ group; and R8, R9 and R10 are independently hydrogen, _ ^^ alkyl, Ci-4 alkoxy, (^ _4 haloalkyl, Or Rbs (〇) n 〇m where m is 0 or 1, η is 0, 1 or 2 JL Rb is C1-4 alkyl or (^ -4 haloxyl; the method includes a compound of formula (11) (where r 1, r 2, R 3, r 4 'R5, R empty' R7, R8, r9 * rkj are all rearranged as defined in relation to formula ⑴), R: R3 (in This paper size applies Chinese National Standard (CNS) _Α4 size (210 × 297 mm) Public interest application _873 Park amendment (I2, 88) Article A8 B8 C8. Application patent scope mi -1¾] 1. A kind of preparation Method for compounds of formula (I): ο (Please read the notes on the reverse side before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ... R1, R2, R5 & R6 are ammonia; r3 & r4 is independently 氲 or methyl; R7 is 卣Element, N02, di-Cwl group; Cm is alkyl or cr.4 ^ group; and R8, R9 and R10 are independently hydrogen, _ ^^ alkyl, Ci-4 alkoxy, (^ _4 haloalkyl, Or Rbs (〇) n 〇m where m is 0 or 1, η is 0, 1 or 2 JL Rb is C1-4 alkyl or (^ -4 haloxyl; the method includes a compound of formula (11) (where r 1, r 2, R 3, r 4 'R5, R empty' R7, R8, r9 * rkj are all rearranged as defined in relation to formula ⑴), R: R3 (in This paper size applies Chinese National Standards (CNS) _Α4 size (210 × 297 mm) A8 B8 C8 D8 39〇873 The scope of patent application '1.' is selected from toluene, xylene, cumene and isopropyl Benzylmethane, hexane or cyclohexyl non-polar solvent, from a cyanide source, alkali carbonate or alkaline earth metal carbonate, selected from the group consisting of four-base ammonium and ammonium salts and phase transfer catalysts and丨 _ In the presence of 6 moles of water, it reacts with the compound of formula (engineering). 2. The method according to item 1 of the scope of patent application, wherein R7 is made of prime or No. 3. According to the scope of patent application scope, A method according to item 1, wherein R 8 is hydrogen. 4: A method according to item 1 of the scope of the patent application, wherein R 9 is hydrogen or (: \ _ 4 alkane group. A method according to item 1, scope of the patent application, where R 10 It is a C h3 SQ 2 group attached to benzyl 4- hydrazone. 6. ^ The method according to any one of claims 1 to 5, wherein the cyanide source is metal detection / cyanide. 7 · The method according to any one of items 1 to 5 of the patent application park, wherein the solvent is toluene 8. The method according to any of items 1 to 5 of the patent application park, in which the phase shift catalyst is tetrabutylammonium bromide., (Please read the precautions on the back before filling this page) Order the Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards -2- The paper Λ degree is in accordance with China Solid Standard (CNS) A4 (210X297 mm)