JPH04501859A - Novel glyoxylates and glyoxylate-activated plant growth regulating activators - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Novel glyoxylate and glyoxylate activated plant growth ijI! 1 activity Drug review history Partial continuation of No. 111 No. 373,210 filed on June 29, 1989 be.

Hatsudara Ω background The present invention provides novel glyoxylates and glyoxylate-activated plant growth regulating activities. Regarding sex agents, more details include 12H-dibenzoCd, g) (1,3) dioxosi ion-6-carvone M# and its derivatives, herein generally referred to as and plant growth regulators and/or pesticides using them. With regard to herbicides, suitable chemicals that particularly affect the growth of grains, ornamental plants and turf crops. plant growth regulators and/or used in combination with carriers and surfactants; It is used as a substitute for herbicides.

Some of the compounds used in the present invention are generally known, particularly When it is a methyl ester it is known from US Pat. No. 3,553,234 There is. This US patent describes 12H-dibenzo(d,g)C1,3)dioxosin. Disclosed is a class of compounds described as -6-carboxylic acids and having the structure: where χ and Y are hydrogen or halogen, and R is hydrogen or lower alkyl. Ru. These compounds are bipolyvidemic agents for warm-blooded animals. emic agents). Pharmaceutically acceptable of these acids The same thing is said about salts. Improved formulation of bipolybideminc agents is disclosed in US Pat. No. 3,941,173 by the same inventor.

Carboxamides are also contemplated in this US patent. However, agricultural It is not suggested for use in the industrial field, and US Patent 3. 553. 2 In testing certain compounds disclosed in No. 34 and No. 3,941.173, However, no herbicidal activity was found.

The present invention describes other closely related compounds falling within the genus of U.S. Pat. No. 3,553,234. does not show much agglomerative activity, whereas selected of the above compounds Expected to be used in controlled doses as a plant growth regulator and/or herbicide. This is based on the discovery that it has unexpected activity.

In the present invention, "plant growth regulator" refers to a plant growth regulator that affects the maturation and metabolism of plants. means a compound or composition. From this, "plant growth regulators" can affect plant growth. It has many influences. However, as any plant growth regulator Active compounds do not affect plants in the same way, e.g. delay or stimulate length and/or stimulate the development of collaterals. By affecting plant growth, and the growth of new shoots, tubers and roots of trees Can prevent new growth such as sprouting and growth of stem buds. Ru. Such conditioners may eliminate early flower blooming, thin out flowers, or Flowering plants can be influenced by increasing the number of flowers. The fruit Fruiting tall shrubs increase the number, size and quality of fruits, produce seedless fruits, completely It can be affected by senescence and acceleration of fruit ripening after ripening. Flowering also decreased This includes selectively controlling the seedling to maturity stage by reducing the can prevent its expansion and also stop normal fruiting. .

Some specific applications of plant growth regulators are as follows.

preventing lodging of grain; Increasing the production of harvestable tea by promoting side shoots, during storage Preventing potato and onion germination, decorative grass areas, parks, golf Fucose and lawns, trees, and irrigation near highways and other public rights-of-way. inhibiting the growth of trees and other vegetation, promoting fruit ripening, thereby assisting mechanical harvesting with one or fewer pickings, mechanical Defoliation of cotton leaves to enable a good harvest, and growth of new growth from defoliated cotton. preventing lengthening and reducing discoloration of mechanically harvested open fibers; Introduced crops such as sugar cane, sugar beet, grapefruit, grapes Increasing the sugar content of cormorant and other fruits, accelerating ripening and cracking the shells. of the nut crop by stimulating delamination and promoting delamination. assisting mechanical harvesting; protecting crops from drought; To promote early dormancy and/or to prevent dormancy from breaking prematurely. Protecting fruit crops from frost by increasing rubber latex flow increasing the seismic resistance of winter grains; Reducing flowering or stand of lettuce, sugar beet and tobacco, tobacco Controlling the suckers of soybeans, peanuts, cotton, tomatoes, melons and Promoting increased fruit set in other fruits, improving fruit color and quality, potted plants , stimulating side shoots such as heather, azalea, chrysanthemum and geranium; Suppresses the growth of potted plants such as poinsettias, petunias, chrysanthemums and azaleas. That, Stimulating the canes of young fruit trees, such as apples and pears.

"Plant growth regulators" can also retard terminal (i.e. vertical) growth of plants. means. In lawns and weeds, the action of this regulator depends on grass height and therefore grass growth. Delay the length. In shrubby plants, on the other hand, such as tomato plants, As a result of the suppression of terminal growth due to the adjustment effect, the growth in the width direction is improved and the desired effect is achieved. You can get results.

1 plate q! L The inventors have discovered the following method of modifying the natural growth and development of plants. sand This method effectively regulates the amount of plants that are not lethal to the area where they grow. It consists of applying a compound of the formula:

Here, A is C0OR, C05RSCONR' R', C5NHw, CN, or When used with one type of B, part of (-0)O-1R is H, Na, di- (CI-C,) alkylammonium, jetanol ammonium, N(3-alkylammonium, mino-propyl) N-oleylammonium, C, -C, alkyl, aryl, heteroaryl, CI-Cs alkoxyalkyl, CI-C, hydroxyalkyl (alkoxycarbonyl)alkyl, dialkylaminoalkyl, cycloa dimethyl, tetrahydrofurfuryl or dimethidioxolanylmethyl.

R' and R' are the same or different, each is H1 lower alkyl, cyclo Alkyl, aryl, heteroaryl, heteroalkyl or alkoxycarboxylic selected from nylalkyl, and NR'R in which these are used together ' is pyrrolidino, piperidino, morpholino, piperazino or N-(lower alkyl Zl! H, CHs , CH3S, CH,S (0), C0OR, B is H1 lower alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, (-0), or A and -C(-0)O-, and Y is H, C, -C, alkyl or alkyl. is X, CF, or X, and X is F, CI or Br; Also, if more than one of Y is other than H on any platform, then this These are in the 3.4.8 and/or 9 positions, with Y on the ring ], 2.10 or If it is in position 11, one or more of Y is not other than H, other aspects , one or more of Y is not other than H on any ring.

According to the present invention, a method has been found for regulating undesirable vegetation growth. This person The method involves administering a compound having the same formula as above in an effective amount that has a herbicidal effect to a place where plants are growing. It is useful especially at the stage from seedling to maturity.

Further according to the present invention, compositions useful for controlling plant growth and development have been discovered. Ta. The composition comprises a compound having the same formula as above, an inert carrier and a surfactant. A preferred embodiment of the above-described methods and compositions according to the present invention comprising In , Y, B and 2 are all H, and the compound has the following formula.

In other implementations of the methods and compositions of the invention, B and Z are all H. is a compound having the following formula.

In yet another embodiment of the methods and compositions of the invention, Y and 2 are all H. It is a compound having the following formula.

The present invention also includes the structure of the following formula: weeding and/or plant growth! Has 11-section activity It contains a novel compound that

Here, A is C00RSCOSR, C0NR' R', C3NH,, CN, or is -C(-0)O- when together with one of B, and R is CI CI alkoxy Alkyl, cycloalkyl, CtCa hydroxyalkyl, (alkoxyal (bonyl)alkyl, dialkylaminoalkyl, tetrahydrofurfuryl and dimethyldioxolanylmethyl, R' and R1 are the same or different H1 lower alkyl, cycloalkyl, aryl, hetero selected from lyle, heteroalkyl, or alkoxycarbonylalkyl or NR' R' is pyrrolidino, piperidino, morpholino, pipepe A saturated monocyclic heterocyclic group such as radino or N-(lower alkyl)-piperazino , Z is H, CH2, CH, S, CH3S (0) or C0OR, B is H1 lower alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy When combined with shi, (-0), or A, it is -C(-0)O-, and Y is H,C , -C, alkyl or alkoxy, CF, or X, and X is F, CI or Br; If one or more of Y is other than H on any ring, they are 3.4.8 and/or in the 9 position and Y is in the 1, 2, 10 or 11 position on the ring. In this case, Y greater than 1 is not other than H, and in other B birch , Y greater than 1 is not other than H on either ring.

Another group of novel compounds within the scope of the invention are those having the formula .

A is C0OR, C03R, C0NR' R', C3NHR, CN, or B's When used with one, it is -C(-0)O-, and R is H, Na, di(C I C4) Alkylammonium, N(3-amino-propyl)N-oleyl ammonium, c, -CI alkyl, aryl, heteroaryl, Ct Cs alkyl Koxyalkyl, C, -C, hydroxyalkyl, (alkoxycarbonyl)a alkyl, dialkylaminoalkyl, cycloalkyl, tetrahydrofurfuryl or dimethyldioxolanylmethyl, and R' and R' are the same or different. and H1 lower alkyl, cycloalkyl, aryol, heteroaryl, respectively. NR', heteroalkyl, or alkoxycarbonylalkyl; R' is pyrrolidino, piperidino, morpholino, piperazino or N-(lower atom) a saturated monocyclic heterocyclic group such as Z is H, CH,, CH, S, CH, S (0), C0OR, and B is H1 low alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, (=O ), or when together with A is -C(=O)O-, Y and W are CI C4 alkyl or alkoxy or CtS, m and n are O-2, m The sum of the last n is 1-4.

Suitable ones for use as A, Z, , B and Y in the composition of the present invention are as follows: It is as follows. Please note that these are listed for explanation purposes only. The invention is not limited.

Simple esters such as: C00CR.

C00CR1CH.

C00CH, CH, CHs COOCH(CHs)t COOCHg CH! CHt CH5COOC(CHs)s COOCH, (CH,), CH.

C00CR, (CH, CH,) CH, CH, CH, CHs The following substitution esters Le: COOCHtCH! OCH5 COOCHz CHt 0CHt CHx CHt CHIcoOcH,CH( OH)CH,OH COOCHt CH-CH! COOCR (CHs) COOCHt CH3COOCHz CHt N ( CHs　tCOOCHl　cHt　N　(CHs)! , HC1 order like Amide: CON　Hz CONHCH.

COHN C & H5 CON (CH,)! Salt like: 0ONa 0OK COOH・(CHs)tNH COOH・(HOCHf CH,)1 NHCOOH-CHs (CHz) t CH=CH(CHm)l NHCH, CH, CHI NH, and the following Other rest like: CH,0H CHt osot C & Hb -CH3-4CM (OH)CN C) (=CHCOOCH□CH.

C.N. C(=S)NH.

C(=O)SCHm CHs c (-0)NHNH!・ Examples of Z include the following.

CH.

CH,S cHw S (0) C(=O)OCHI CH3 Examples of B include the following:

CH.

C: Hs CHw C.F.

CH, C(=o)o- =0 (CI(3)! CHCOC(-0)-Lactone(B+A) Examples of Y include the following:

CH.

(CH,),C C.I. O CH,O Ch　Hs　CHt　O CH3C (=O) O No.

Nitrogen ring structures such as piperazine derivatives These and other aspects of the invention are As will be apparent to those skilled in the art from the following description of the specification and claims. cormorant.

Exorcism of Fireflies In the present invention, the term "plant growth regulator J" or "plant growth regulating effect J" means When applied to a vegetated area, grains such as those described with the previous examples , refers to the ability of glyoxylates to influence the growth of ornamental plants and lawns. It is something. Target plants, selected glyoxylates and their application methods , the amount and timing of application can have varying effects, taking into account other circumstances. .

In general, the effects obtained by applying glyoxylates are is a morphological process, a desired enhancement, suppression and/or change. like this Examples include acceleration or retardation of leaf, shoot and root growth, reduction in height, branching, Increased axillary buds, suppressed terminals, and suppressed regrowth after pruning (reducing the need for later pruning) (reduced), enhanced root growth, delayed germination, increased root number, and increased yield. Ru. In particular, the glyoxylates of the present invention are suitable for use in perennial ryegrass, young, tall grass. Commonly used in grasses of the genus Estoca and grasses such as Kentucky bluegrass. It has been found that when used, it is an effective growth inhibitor. Shows plant growth regulating effects Another example is preferably No. 2 or No. 2 as a straw shortening agent for wheat. This is the ability of the glyoxylate compound obtained when it is used in the third growth stage, This is especially useful when high levels of nutrients are used to increase grain yields. It is.

[When we use the term herbicide J or "herbicidal effect J," we mean glyoxyl to at least substantially suppress its growth. It means that the compound is commonly used. A particularly important example is grass in wheat. To regulate overgrown weed growth and reduce flowering of standing wheat beet The method is to use a type of glyoxolate. Glyoxylate is a nut When applied to the soil where the tubers begin to germinate, the semen, which is generally considered difficult to adjust, It has been found to be particularly useful in regulating the growth of sagebrush, especially yellow sagebrush.

Compounds useful in Uni are those having the structure:

Each defined glyoxylate compound has a herbicidal and/or plant growth m* effect. It was found that it has. glyoxylate in addition to considering activity and selectivity. A particular ester or salt form is often selected for convenience in handling and usage. It will be done. Examples include n-butyl esters (which reduce volatility). Examples include those selected from methyl esters) and methyl esters. On the other hand, volatilization If this is desired, for example to induce branching of houseplants, More volatile nitriles and lower Compounds such as esters such as methyl, ethyl and propyl esters are preferred. be used properly.

On the other hand, the selection of substituents placed on the benzene ring affects the nature of the plant growth regulating effect obtained. Although likely to affect the quality and scope of the substituents, such substitutions may (1) uniqueness, (2) position on the ring or rings, and (3) number of substituents to be accommodated. limited in relation to. The substitution opportunities are 1.2.10 and 1 according to the following number system: Particularly restricted when placed in 1st place 1st place.

In this case, substituting methyl groups at more than one position can significantly impair the herbicidal effect. I found out. Growth inhibition and / or change the remaining benzene ring positions (3, 4, 8 and and 9) are more likely to be replaced. Each ring is on the ring Although it is preferred not to substitute at more than one position, the choice of substituents is as described above. The amount may be increased.

Glyoxylates are generally used as carriers and surfactants, i.e. dispersing, emulsifying or or applied to the land where plants grow as an active ingredient in a composition containing a wetting agent.

It also includes diluents, additives, and other active ingredients for different or complementary uses. The composition may contain certain finely divided solids, granules, wet It is used in the form of wettable powders, solutions and dispersions.

Inert carriers include solids, such as clays, natural or synthetic silicates, tars, etc. liquids such as water, alcohols, esters, aromatic hydrocarbons, petroleum frac Examples include tion. Surfactants can be anionic, cationic or non-ionic. On-type ones, such as salts of gutsulfonic acid, alkylarylsulfonic acid, etc. acetates of alkylamines, and ethylene oxide and aliphatic alcohols or or acid condensates. Furthermore, the composition has a thickening side, an adhesive side, a stable side, Preservatives and other adjuvants known in the art may also be included.

Glyoxylates can be prepared using conventional techniques such as sprinkling, pine dew or spray or greying. smoke bombs (smoke pumps) in closed spaces such as houses. Depending on the method used, it may be prepared in various forms, such as solutions, suspensions, wettable powders or It can be applied in the form of granules.

The compositions of the invention generally contain 5 to 95% by weight of active glyoxylate compound. and when applied as a herbicide, 0.0% per hectare. 5 to 4 It is applied at the rate of kg. On the other hand, when used as a plant growth regulating composition, the active The amounts of ingredients are relative and the amount used will depend on the particular glyoxylate and per hectare, although this varies greatly depending on the It ranges from 0°01g to 4kg. Depending on the type of plant to be treated, Conveniently, a solution containing 0.1 to 500 ppm of the active ingredient is added until the water is washed away. It can be conveniently applied by spraying.

Some of the compounds that are the subject of the invention can be prepared by methods known in the art, e.g. Derived from the acid form that can be prepared, for example, according to U.S. Pat. No. 3,836,543. Can be done. One substituent on the benzene ring is described in the aforementioned U.S. Pat. No. 3,836,543. Variations on these methods when substitution is desired at the 12-position Improvements are illustrated in the examples below. These acids are then used, e.g. When producing grade alkyl esters, the final form is prepared according to conventional esterification. can be converted into compounds.

For those skilled in the art to better understand the present invention, preferred embodiments and descriptions of the present invention will be described. The present invention will be explained in more detail with reference to the following examples, and its effects. .

synthesis practice snoring 12I]-dibenzo d 3 dioxosine-6-carvone air driven over 2.2' in a 12 liter three-necked flask equipped with stirrer and condenser. - Methylenebisphenol (200.24g, 1.0m.

1), 4 liters of isopropyl alcohol and potassium carbonate (552,84 g, 4.0 mol) was added with stirring. Dichloroacetic acid (82.5 ml, 1 ゜0mo+) is added over a period of 2 minutes. Foaming occurs during addition of dichloroacetic acid is observed. The reaction mixture is a heterogeneous white mixture that is easily stirred, but This is heated under reflux and vigorous stirring. After 24 hours, the reaction mixture was allowed to reach room temperature. Cool and add additional dichloroacetic acid 82. 5ml (1,0mol) was added Ru. Some bubbling is observed again. The reaction mixture was then further heated under reflux. Heat for 72 hours. Total reflux time is 96 hours. During total reflux After 48 hours, the reaction mixture became viscous and vigorous stirring was continued. Ru.

Once the 96 hours of reflux was complete, the distillation head of the condenser was replaced and the 200 l of isopropyl alcohol was distilled off under normal pressure and placed in 200 ml of H,O. Change. This is repeated until the distillation temperature reaches 95-100°C. This steam Throughout the distillation process, once H,O is added, the reaction mixture becomes more fluid; As a result, a reddish-brown homogeneous solution is obtained. Distillation temperature is 95-100°C Once reached, the reaction mixture is cooled to room temperature. When cooled, a solid is formed It is important to keep stirring vigorously.The reaction mixture is then diluted with concentrated hydrochloric acid (800 m Strongly acidified by carefully adding 1) over 1-2 hours. foamy Therefore, utmost care must be taken during the addition of hydrochloric acid. This bubbling is especially caused by the addition of hydrochloric acid. It becomes especially intense in the later stages. After HCI was added, the reaction was continued for an additional 2 hours at room temperature. This is done by stirring for a while. Solids are collected by filtration and thoroughly washed with H,O. .

These solids were then dissolved in 2 liters of ethyl acetate and 2 liters of 1N HCl. and placed in a separatory funnel with vigorous stirring. The organic layer is separated and brine , dried over MgS Oa and concentrated. solid obtained was then dried in a vacuum oven to yield 239 g (93 g) of crude product as a brown solid. %) was obtained. This product is then placed in a Soxhlet extractor and extracted with cyclohexane. (211 notres) is thoroughly extracted with reflux. This cyclohexane solution is The mixture is cooled down and the precipitated product is filtered off. Extraction speed is cyclohexane It all depends on how vigorously they are refluxed and recycled. in this way and 12H-dibenzo(d,g)(1,3)dioxosine-6-carboxylic acid 14 7 g are obtained as a white solid.

mp 153-157℃; TR (KBr) 5.7B, 6.76, 6゜93 , 8.12, 10.1, 13. 1cm-';'HNMR (60MHz, DMSOdi) 3.64 and 4.38 (2d, 2, CH.

), 5.09 (s, 1, CH) 6.9・-7,6 (m, 8, Ar-old . Product purity as determined by liquid chromatography is greater than 99%.

Example I n-Butyl 12H-diben'd 3 dioxosine-6-carboxylate 5001 round with stirring bar and Dean-3tark device In a bottom flask, add crude (87% ) 12H-dibenzo(d,g)(1,3)dioxosine-6-carboxylic acid 111 ．． 4g is placed. The mixture was stirred at room temperature for 15 minutes until the acid was completely dissolved. Concentrated sulfuric acid (4.0 ml) is then added and the reaction mixture is heated to reflux.

As soon as reflux is reached, an aqueous layer begins to separate in the Dean-Stark apparatus. 2 o'clock After refluxing for a while and no water formation is observed, cool to room temperature in a cold water bath. It will be done. A total of 12 ml of water is collected. Most of this water is refluxed for 30 minutes is generated. The cooled red-yellow reaction solution was diluted with 200 ml of toluene, Washed with 30 ml of water, 300 ml of saturated aqueous NaHCOs solution, 300 ml of brine. and then concentrated under reduced pressure on a rota-vap.

Toluene (200 ml) is added to the residue and the solution is concentrated again under reduced pressure. . This evaporation with toluene facilitates the removal of n-butanol. the residue obtained was placed in 300 ml of 2:1 toluene:ether and 5% NaOH20 (ls Washed with l. To break the emulsion produced by washing with 5% NaOH Brine 50a+1 is added to. The organic solution was then washed with 200 ml of brine. Washed, dried over MgS Og and concentrated under reduced pressure to a thick light 130 g of a bright red-yellow liquid are obtained. This liquid is then used as a distillation head. Distilled under vacuum using a Zen adapter and an oil bath for heating. during distillation, distillation Care is taken to prevent the product in the capacitor from solidifying. to 0.25++- A residue (11 g) with a boiling point of 70°C - 170°C is collected at 0 then Pure as a thick clear liquid from boiling point 171°C-180’C at 0.25v++ 84.3 g (62%) of n-butyl ester are collected. This increases in capacity when cooled. It solidifies easily to give a white solid.

mp63-66°C (softened at 60°C); 99% purity determined by L,c. Above, bp189-195°c10.4! IN; IR (neat,) 3. 45.5.75, 6.95, 8.35, 10. 4cm-'HHNRM (6 0MHz, CDCl5) 0.9 1.9 (m, 7, OCH, CHl C H, CH3), 3.42 and 4.6 (2d, 2, Dan and L), 4.35 , (t, 2, Oq几, CHI CHl CHI), 5.05 (s, 1, CH) 7.0-7.4 (m, 8, Ar-H)).

result of analysis C+ q H! . Calculated value as 04: C, 73, 06i H, 6, 45 actual measurement Value: C, 73, 0; H, 6, 7 length Ethyl 12H-ku 5 otorigami-113 dioxosine-6-carpoxylene 2-1 12H-dibenzo(d,g)(1,3)dioxo in 215 sl of ethanol -6-carboxylic acid (31.8 g, 0.124 mol) and concentrated sulfuric acid (1.6 ml) is heated to reflux and the condensate is passed through a 4A molecular sieve. 2 hours later , the reaction solution was cooled to room temperature, 100 liters of methylene chloride was added, and then is neutralized by the addition of solid NatCOs. The salts are removed by filtration and the filtrate is concentrated. The residue was taken up in CHzCIg and diluted with water, 5% aqueous NaOH and buffer. line washed, dried over MgSOl, and condensed to a white solid. 31.1 g (88%) of the product are obtained as a solid.

mp 86.5-88.5°C; IR (KBr) 5.63, 6.7, 6°8 8, 7. 2, 8. 12, 8. 98, 9. 25, 10. 1 cm-' Trans-HNMR (60MHz, CDCIg) 1. 4 (L, 3, C Hl), 3.43 and 4.6 (2d, 2, CH,), 4.42 (q, result of analysis C3) Total as H,,O,’lt4M: C,71,82; H,5,67 real Measurement f1: C, 71, 7i H, 5, 8 implementation square Methyl 2H-diben d 3 dioxosine-6-carpoxylene Production is carried out in the same manner as in Example 3 except that methanol is replaced with ethanol.

The product obtained is a white solid.

mp 107-110'C; IR (KBr) 5.69, 6.77, 8°2, 9. 3, 10. 05 C11-';'HNMR (60MHz, CDC 1,), 3,5 and 4.62 (2d, 2, CHl), 3.98 (S , 3, CHff), 5. 1 (s, L CH) 7. 0-7.　 5 (m, 8, Ar-H).

result of analysis Calculated value as C+ b H+ s O-: C, 71, 10; H, 5, 22 real Measured values: C, 71, Oi H, 5, 1 implementing physician i n-propyl 12H-dibenzo d geo゛shin-carbodon-no-nijo Same as Example 3 except using the same amount of n-propatool instead of ethanol. The preparation is carried out as follows to obtain a white solid.

mp82-85"C; IR (KBr) 5.7, 8.35, 9.4.10.1 5cm = Goose; 'HNMR (60MHz,, CDCl5) 1゜05( t, 3, CH3), 1.95 (m, 2, CHI C and t CH.

), 3.47 and 4.65 (2d, 2, CHI), 4.33 (5 result of analysis Calculated value as C+sH+sOa: C, 72,47, H, 6,08 actual measurement ([: C, 72, 7; H, 6, 0 back Iso-propyl 12H-dibenzo d-dioxine-carboxylate The main procedure was carried out in the same manner as in Example 3 except that isopropanol was used instead of ethanol. The title product is prepared and a white solid is obtained.

mp94-97°C; IR (KBr) 5.73, 6.78, 8.25, 9. 05, 9.4, 10. 1 C11-';'HNMR (60MHz, CDC l5) 1.4 (d, 6, CH-(Cl,)3), 3.46 and 4 ．． 6 (2d, 2, CH,), 5.03 (s, 1, 0-CH-0), 5 ．． 25 (m, 1, CH (CHs) *), 6. 9-7.5 (m, 8, Ar　H)i+ result of analysis Calculated value including C+sH+sO-: C, 72,47; H, 6,08 Actual value: C, 72, 4i H, 5, 9 implementation base I L-butyl 12H-dibenzo d 13 dioxosine-6-carboxylate 12H-dibenzo(d,g)(1,3)dioxoxy in 45ml of thionyl chloride A solution of 6-carboxylic acid (3,0 g, 0.0117 mo+) was heated under reflux. Ru.

After 4 hours of reflux, excess thionyl chloride was distilled off under atmospheric pressure and then evaporated under vacuum. thionyl chloride is removed. The obtained acid chloride was dissolved in 35 ml of toluene. N,N-dimethylaniline (1,8m+, 0.01 ．． 405rnol) containing t-butyl alcohol (15ml NI solution) . After stirring at room temperature for 23 hours, the reaction mixture was ampered under reduced pressure and the resulting residue was evaporated into ethyl alcohol. acetate, washed with water and brine, and poured onto MgSOl. and concentrated to give a syrupy residue with a yield of 3.4 g. Dora column chromatography (elution with 1:4 ethyl acetate-hexane) ) gives 1.57 g (43%) of product as a white solid.

mp94-97°C; IR (KBr) 5,75, 8.22, 8.7.9.4 3, 10.22, 13. 21c+s-';'HNMR(60Mt(z , CDCl3) 1.6 (S, 9, C(CHx) s), 3.4 5 and 4.6 (2d, 2, CHt), 4.93 (s, L CH), 6, 95-7. 4 (m, 8, Ar-H).

result of analysis Calculated value as C+ * Ht o Ot: C, 73,06, H, 6,45 real Measurement 4M: C, 73, O; H, 6, 3 tumbler n-octyl 12H 2nd grade 1-13' dioxosine-6-carbo0 g, 0.0156 mn+) and thionyl chloride 45-1 as in Example 7. Distilled under reflux. The acid chloride was then dissolved in 50 ml of toluene and n-octyl J Real containing ethylamine (2,0-1,0,0187 mol) Add dropwise to Cole (20 ml) solution over 10 minutes. After stirring at room temperature for 20 hours, The generated insoluble matter is removed by filtration, and the filtrate is concentrated under reduced pressure. the residue obtained was removed into CHC1, washed with HtO1 then brine, and Mg Dry over SOI and concentrate. The resulting residue was subjected to dry column chroma purified by chromatography (elution with 1:10 ether-petroleum ether). , 4.18 g (73%) of product are obtained as a clear syrup.

IR (neat) 3.42, 5.63, 6.71, 6.87, 8°95 , 10.1 cm”; 'HNMR (60 MHz, CDC13) 0.9-2. 0 (m, 15, 0CHt (CHz)) b (C and )), 3°48 and 4.62 (2d, 2, CHz), 4.35 (t, 3, analysis results C,,H□0. Calculated value: C, 74, 97i H, 7, 66 Actual value: C, 74, 6i H, 8, 2 implementation tithe 1 1-bu-xyelyl I H-dibenzo d-dioxine--carboxylate Crude 12H-dibenzo(d,g)(1,3)dioxocin-6-carbonyl chloride ( 4.8 g, 17.5 mmol) was dissolved in toluene and incubated at 0 °C under argon. 2-butoxyshetanol (2,77ml 1.21mmol) in toluene and 5ml of triethylamine. This mixture was heated under reflux for 2 hours. , then cooled to room temperature. This mixture was poured into 150aI of water and 4X1 Extracted with ethyl acetate. The organic solution was 5% hydrochloric acid, 5% sodium hydroxide. Washed with thorium then brine, dried over magnesium sulfate and filtered. Ru. When the solvent is removed, a yellow liquid remains, which is purified on a dry column silica gel. Chromatographed using ethyl ether/hexane (1F2) as solvent. A yellow oil (4.3 g, 69%) is obtained. ￥I1 layer chromatograph Purified products with analytical precision can be obtained by using

IR (neat) 1770, 1582 c1';'HNMR (CDC1 s) 0.75 1.3 (m, 3H, CH,), ], 2-2. 0(m, 4 H, CH,), 3.3 4.0 (m, 5H, OCHm and Benzilink) , 4.4-4.9 (m, 3H1OCOC, H! and Benjiric), 5 ．． 6 (s, IH, CH), 6.9-7.5 (m.

8H1 Aromatic).

result of analysis Calculated value as Ct + Hz - Os: C, 70,7; H, 6,79 actual measurement Value: C, 70, 4; H, 6, 9 execution scale l Cyclohexyl 2H-dibenzene-6-cal Crude 12H-dibenzo(d,g)(1,3)dioxocin-6-carbonyl chloride ( 4 g, 14.5 mmol) was dissolved in 45 ml of toluene and heated under argon to 0 3 ml of triethylamine and cyclohexanol (1,75 g, 17.5 m m.

1). The mixture was heated under reflux for 2 hours, cooled and diluted with 5% hydroxide. washed with sodium chloride, then brine and dried with magnesium sulfate. filtered. When the t8 medium is separated, a brown liquid remains, which can be used as a solvent. Chromatographed on dry column silica gel using thyl ether/hexane. Upon treatment, a yellow solid separates. This solid is decolorized with charcoal, leaving a gray solid. Obtained (4.32 g, 87.7%).

mp 120-125°C; IR (KBr) 1755, 1580cm-' 'HNMR (CDCIs) 1.02.4 (m, IIH, cyclohexyl ), 3.37, 3.6, 4.51 and 4.73 (q, 2 skin Hz), 5 ．． 05 (s, IH, 0CR), 6.9-7.45 (m, 8H, aromatic ).

result of analysis Calculated value as Ct + Ht t O-: C, 74, 54H, 6, 55 actual measurement (1: C, 74, 3i H, 6, 6 implementation 1- Mengami Tanwashi tl177u) τle 12H-dibenzo d 3 dioxocinni 6- carboxylate Crude 12H-dibenzoCd, gl (1,3)dioxocin-6-carbonyl chloride (4.25 g, 15 mmo+) in a toluene solution with tetrahydrofurfuryl alcohol. A toluene solution of triethylamine (8+il, 18mrno+) and 3ml triethylamine is Add slowly under nitrogen atmosphere at 0°C. This mixture was heated under reflux for 1 hour. cooled and treated with water and ethyl acetate. Organic layer is 10% hydroxyl washed with sodium chloride, then brine, dried over magnesium sulfate, and filtered. be done.

When the solvent is removed, a yellow liquid remains, which is ethyl acetate-hexane as the solvent. Chromatographed on dry column silica gel using Sun. obtained When the oil (still yellow) is bleached with charcoal and solidified, a white solid forms. (4.12g, 78%).

mp83-85°C; IR (KBr) 1760, 1580 cm-';' HNMR (CDC1i) 1.6 2.4 (m, 4H, CHt), 3.35, 3.57, 4.5 and 4.71 (q, 2HS CH,), 3.7 4.1 (m, 2H, CHzO), 4. 1-4.5 (m, 3H1OCH, CHO) , 5.1 (s, LH, CH), 6.95-7.5 (m, 8H1 aromatic ).

result of analysis Calculated value F as CtoHtOCh C, 70, 5B, H, 5, 92 actual measurement value: C, 70, si H, 5, 9 implementation box l Ethyl 12H-dibenzo d 13 dioxocin-6-thiocarboxylate 12H-dibenzo(d,g)(1,3)dioxosine-6-carboxylic acid (1g1 3.9 mmo+) and ethanethiol (0.8 ml, 5.9 mmol) at -25°C Add dicyclo to dry tetrahydrofuran 12+*1 solution under argon atmosphere. Hexylcarboximide (DCC 22g, 9.8mmo+) is added. child The mixture is stirred at -20°C for 2 hours and then left in the refrigerator overnight. this The mixture is then warmed to room temperature and added with oxalic acid to destroy excess DCC. An aqueous solution is added. This mixture is then diluted with ethyl ether and filtered. . The solids are washed with ethyl acetate and the filtrate is separated. Organic layer is 10% hydroxyl The organic solution is washed with sodium chloride, then twice with water, and once with brine. The liquid is dried over magnesium sulfate and filtered. Remove the solvent and leave a yellow viscous get oil. This oil was prepared using ethyl acetate/hexane (1:2) as a solvent. chromatographed on a dry column of silica gel to produce a yellow viscous oil (8 90 mg) is obtained. This oil is solidified in petroleum ether to obtain a white solid.

mp 77.5-79°C; IR (KBr) 1690, 1000, 758 0cm-';'HNMR (CDC1z) 1. 2 +,, 6 (t, 3H, CH,), 2.82 3.28 (q-2H, SCH, 3°37 , 3.58, 4.49 and 4.69 (q, 2H, CH,), 4.99 (s, 11-T, CHO), 7. 02-7. 45 (m, 8H, aromatic ).

result of analysis Calculated value as auto-HlioxS: C, 67, 9B, H, 5, 37 Actual measurement value: C, 67, 8i H, 5, 5 husband treatment upper 1Δ 12H-dibenzo d 13 dioxocin-6-thiocarboxyamide 12H-dibenzo(d,g)[1,3)dioxosine-6-carboxamide ( 3.88g, 0.0152mol) and Lawesson's reagent (Lawesson'sr agent, 3.69g, 0.00912mol) in 40+al) toluene solution is heated to reflux and stirred. After 2.5 hours, the reaction system was cooled to room temperature and am at reduced pressure to give a dark gummy residue. This thing's Francie chromatograph Perform fee (dissolution Ws with CH, CI!) to obtain 1.6 g of product as a gray solid. .

Recrystallization from hexane gives 1.1 g of product as a gray solid.

mp 165-169°C; IR (KBr) 3380, 3140. 161 5, 1440. 1220, 975 C11-';'HNMR (DMSO- d,) 3.65 and 4.41 (2d, 2, 12a and] 2b), 5. 17 (s, 1, H6), 7.0-7.6 (m, 8, Ar-H).

result of analysis Calculated values as C,, H,, NO, S: C, 66,4; H, 4, 8N, 5. 2 Actual value: C, 66, 5; H, 4,912H-dibenzo (d, g) (1, 3) Dioxocin-6-carboxamide (8.24 g, 0.0323 mol) and Pi Lysine (5,74m1.0.071m.

l) O′C11,4-dioxane 80+1 solution with stirring trifluoroacetic anhydride (5.0 ml, 0.0355 mol) is added. After stirring for 5 minutes at O″C, The reaction system is warmed to room temperature and stirred for 3 hours. The volatiles are removed under reduced pressure and the residue is taken up in ethyl acetate, IN HCI, H, O1 saturated N a HCOx by washing with aqueous solution, brine, drying over MgOJ, and concentrating. 6.8 g of a white solid is obtained. When recrystallized from cyclohexane, it is produced as a white solid. 5.46 g (70%) of product is obtained.

mp 127-130°C; IR (KBr) 6.2B, 6.71, 6°8 5, 7. 44. , 8. L 8. 45, 8.96, 13. 1 c+s -';'HNMR (60MHz, CDCl5) 3.83 and 4.29 (2d , 2, CHz), 5.84 (s, 1, CH), 7. 2-7゜0 ( m, 8, Ar H) * result of analysis C+s H+N Calculated value as Ox: C, 75,94; H, 4°07 N, 5.90 Actual value: C, 75, 8i H, 4, ON, 5.9 Twisted 1 soil 12H-dibenzo d 13 dioxosine-6-carvone one life 12H-dibenzoCd, g) (1,33 dioxosine-6-carboxylic acid (1°3 g, 0.00507 mol) and NaOH (0.41 g, 0.0101 mol). The methanol 5(1+l) solution is refluxed for 30 minutes. The reaction mixture is then evaporated under reduced pressure. When the residue is recrystallized from ethanol-water, the product is a white solid. 0.65 g (45%) is obtained.

mp 320°C or higher; IR (KBr) 3.0, 6.2, 7.0.8.25 , 8.35, 10.45, 13. 3cm-'B'HNMR (60M Hz, DxO) 3.3 and 4.4 (2d, 2, CHt), 4.8 ( s, L CH), 6.8-7.4 (m, 8, Ar-■).

result of analysis Calculated value as C15HIIOa N a ・l / 2 Hl O: C, 6 2,7i　H,4,2 Actual value : C, 63, O; H, 3, 9 implementation 12H-dibenzo d 13 dioxosine-6-carvone potassium 12H- Dibenzo(d,g)(1,3)dioxosine-6-carboxylic acid (5°0g, 0. 0195mo+) and potassium carboxylate (1.95g, 0.0195mol) The mixture in 100 ml of water was stirred at room temperature for 4 hours and then at 45°C for 2 hours. It will be done. The reaction mixture is then cooled to room temperature, treated with charcoal, concentrated, and then A moist gray solid is obtained. When this substance is recrystallized from ethanol, it becomes a whitish-gray solid. 2.27 g (39.5%) of body product are obtained.

mp 275-290℃; IR (KBr) 2730-3600, 161O 1980, 760 cm-';'HNMR (CDCIs) 3.5 and 4.3 5 (2d, 2, CHg), 4.5 (s, 1, Ha), 6.8-7. 5 (m, 8, Ar H) @Analysis results C+sH1+Oa K・1/2 Ht Calculated value as O: C, 59, 4;H,3,99 Actual value : C, 59, 2 + H, 4, 5 Implementation team completed 12H-Dibenzo d 13 Dioxosine-Carvone die 22411z salt 12H-dibenzoCd, g) (1,3)dioxosine-6-carboxylic acid (4°O g, O, O156 mol) in tetrahydrofuran 40-1 with stirring. Nolamine (1.64 g, 0.0156 mol) is added. 2 hours at room temperature After that, the produced solid was collected by filtration, washed with ether, and dried to obtain a white solid product (5°). 04 g (89%) are obtained.

mp 114-116°C; IR (KBr) 3.0-4.0, 6.25.6 ．． 79, 7.05, 8.1, 10. 35cm-';'HNMR (60M Hz, DMSO-dh) 3.05 (m, 4, (CHI CH, 0H)z ), 3.55 and 4.37 (2d, 2, CHm), 3°75 ( m, 4, (CHI (precept x OH) z), 4.69 (s, 1, CH), 6. 4-7.5 (m, 12, Ar-H and 4 exchangeab le).

result of analysis Calculated values as C=-HtsOh: C, 63, 15, H, 6, 41N, 3.　 88 Actual value: C, 63, 2i H, 6, 4N, 4.0 Tips and Tricks 11 11 ■ Ninohenzo d 13 Dioxosine-6-carvone dimethylimae salt 12H-dibenzo(d,g)(1,3)dioxosine-6-carboxylic acid (5g, 19.5 mmol) of ethyl acetate/benzene solution was dissolved in excess at O'C under nitrogen. Added to liquid dinotylamine. The mixture is stirred at room temperature under nitrogen overnight.

The resulting solid is filtered and dried to obtain 5.5 g of a white solid.

mp 164-172°Cr IR (KBr) 1640cm-'i'HN MR (CDCIs) 2.51 (s, 6HS NCH3), 3.47. 3.6, 4.25 and 4.4 (q, 2H, CH,), 4.55 (S, IH , CHCO, ), 6. 8-7. 5 (m, 8H1 aromatic).

result of analysis Calculated value as C, 7HI 90-N: C, 67, 76i H, 6, 36N ,4. 65 Actual measurements: C, 67, 7i H, 6, 5N, 5. 0 Shout- 4-p 2-dimethyl-13-i oxonyl methyl 12H-dibenzo d.

-6 two-m1n-≦nbajsu2jni-6-cal-12H-dibenzo (d, g) (1,3)dioxosin-6 = carbonyl chloride (IOg, 39 mmol) Glycerol ketal (5°6 steel!, 45 mmol) dissolved in toluene and triethanolamine 10+1 in toluene at 0-10°C under argon atmosphere. Added below. The mixture was heated under reflux for 5 hours and then cooled to room temperature. Pour into 100+ ml of water and extract 4 times with 15 Q ml of ethyl acetate. be done. The organic solution was washed with 5% HCI, 5% NaOH, then brine, and sulfurized. Dry with magnesium acid and filter. The solvent is removed and the residue is Dry column silica gel using ethyl ether/hexane (1:1) as Chromatographed above to obtain a yellow liquid. Crystallize this in petroleum ether The resulting solid is filtered and washed with petroleum ether to yield a white solid. It will be done.

mp 109 111°C; IR (KBr) 1780, 1581cr1; Low HNMR (CDCI2), 1,4 and 1.47 (2s, 6H, CH,) , 3.36, 3.58 4.49 and 4.7 (q, 2H, CH,), 3 ．． 7-4.4 (m, 3H, CHO and CH, O), 4, 4-4. 6 ( m, 2H, OCR,), 5.1 (s, IH.

0CHO), 6. 95-7. 45 (m, 8H, atl?tic).

result of analysis Calculated value as Cg+HzOa: C, 6B, to; H, 5,99 Actual measurement value: C, 68, 3i H, 6, 0 implementation u top l Methyl-6-methyl-12H-dibenzo d3 dioxosine-6-carboxy Sylate Drying of isopropylcyclohexylamine (2,92ml, 0.0178mo+) 15 ml of dry tetrahydrofuran (THF) O’C,N! Add n-B to the stirring solution below. uLi (11.84 ml of 1.5M in hexane) is added. 15 at 0°C After stirring for a minute, the solution was cooled to -65°C and the methyl 12H-dibenzo(d,g) (1,,3) Dioxosine-6-carboxylate) (4,0g, 0.0148 A solution of mo+) in THFI21 is added dropwise over a period of 5 minutes. This solution was heated to -65°C. Stirred for a further 10 minutes, then methyl iodide (1,84 m1.0.0246 m Add syringe to 25 ml of dry dimethyl sulfoxide solution of o+) for 2 minutes at room temperature. Added by di. After stirring for 30 minutes, the reaction mixture was CHtCI!　30 Diluted with 0tl, washed with MCI of H,01IN, then prine, Mg Dry on S Oa and am. The resulting residue was subjected to dry column chromatography. purified by chromatography (eluted with 1:4 ethyl acetate/hexane), yellow Obtain 2 g of colored syrup. This product was purified by HPLC (water 500.2 columns, 4 cycles). 1;7 eluted with ethyl acetate/hexane) to produce a clear syrup. 1.1 g (26%) of product was obtained.

IR (neat) 5.65, 6.3, 6.7, 6.85, 7.25 cm- '; HNMR (60MHz, CDC1t), 1.36 (S, 3, CHs ), 3.71 and 4.32 (2d, 2, CHt), 3.9 (s, 3, 0CHs), 6. 95-7. 4 (m, 8, Ar-H).

result of analysis Calculated value as Cl, H+-Os: C, 71,82; H, 5,67 Actual measurement: C ,7],,8i H,5,7 length ■ Matata cis and tones methyl-12-methyl-12H-dibenzo dl 3 di Oxocin-6-carboxylate 2.2'ethylidene bisphenol (10g , 0.0467 mol), dichloroacetic acid M (3.85 tl, 0.0467 mol) and potassium carbonate (25.8 g.

A mixture of 200 μl of isopropyl alcohol solution of 0.187 mol) was heated under reflux. was heated with vigorous stirring for 24 hours, after which 3.85 ml of dichloroacetic acid was added. and the mixture is then refluxed under stirring for 70 hours. Isopropyl alcohol 0 reaction mixture, in which mol is removed by distillation under atmospheric pressure and gradually replaced by H,O. The compound was cooled, acidified by the addition of concentrated hydrochloric acid, and extracted into chloroform. Ru.

The chloroform extract was washed with brine, treated with charcoal, and purified on Mg5OR. Dry and reduce to 111 tl to obtain a quantitative amount of crude acid. This thing then fiH in methanol solution (100 ml) for 2 h in the presence of zso4 (0,6 ml). It is converted to its methyl ester by refluxing. The solution is cooled and C)(, Cl350-1 is added and the mixture is mixed with the addition of solid N a t CO- neutralized by

Inorganic salts are removed by filtration and the filtrate is concentrated to contain CHtCI. taken, washed with brine, dried over MgS Oa, and reduced to 11 11.5 g of a dark semi-solid are obtained. The product was subjected to dry column chromatography ( 1;4 By treating with ELOAc-hexane solution #), it can be made into a product. 5.0 g of a white solid product consisting of a 1:1 mixture of trans and trans isomers (38%) get it.

mp95-120°C; IR (thin film) 5.62, 6°7, 6.9, 8.2, 9.25, 10.05, 13. 05 cm-'; 'HNMR (60MHz, CDCl　s), 1.66 and 1.89 (2 d, 2, CHs), 3,88 and 3.95 (2s, 3, 0CHff) , 3,95 and 5.1 (2q, 2, CH), 5.0 and 5.36 (23, 1, CH),? , O-7.5<m, 8, Ar-H).

result of analysis CI? Calculated value as HI & Os: C, 71, 82; H, 5, 67 Actual measurement value: C, 71, 6i H, 5, 7 on NI Meng Chi 411 Nijime Lou H-dibenzo 1i-1L work one shadow Lzt previous Zushin-6 -carboxylate 2.2'-isopropylidene bisphenol (3,65g, 0.01594rn o1), potassium hydroxide (85% solution, 2.68g5O, 0478mol and Isopropyl alcohol of dichloroacetic acid (1,3]rin 1.0.O1594mol) The mixture in 65+el is heated under reflux. 85% KOH after 24 hours of reflux 1.79 g of dichloroacetic acid and 1.31 liters of dichloroacetic acid were added, and the reaction mixture was refluxed. It will be heated for 2 days. The resulting reaction mixture was then diluted with 200 Jll of water, Acidified by addition of salt M (10ak) and extracted into ethyl acetate. Served. The ethyl acetate solution was washed with brine and dried over MgOa. and concentrated. The residue is washed with petroleum ether to give a reddish-brown syrup. Obtain 3.7 g of crude product. This material is then processed through esterification, saponification, and esterification. It is purified by steps (esterification agent, methanol, H, So, etc.). dry column Chromatography yields 0.97 g of crude product. This is saponification (NaOH, MeOH-H2C), and purified by dry column chromatography, White solid 0°6OR. Esterification of this product (EtOl(,H,So,) and preparative IN chromatography (I:4 ethyl acetate-helical Purification by solution H) with xane yielded 0.25 g of a clear syrupy product. Ru.

TR (neat) 3, 34, 5.56, 6.95, 8.2, 13゜2c '; HNMR (CDCl3), 1.28 (t, 3, CH1 Dandan,), 1.75 and 1.9 (2s, 6, (CHs)t C), 4°24 (q , 2, and, CHI), (sl 1, CH), 6. 9-7゜6 (m, 8.A r H); m/e 312m analysis results C,,H,. Calculation as 04 41: C, 73, 06; H, 6, 45 actual measurement value : C, 72, 4; H, 5, 7 Example set λ -12H-dibenzo d 13 dioxocine-12-hydroxy 6-left stop ± 2 acid i upper Z 12H-dibenzo(d,g)(1,3)dioxocine-12-keto-6-carbo acid (1,0,0g, 0.0370mo+) and sodium hydroxide (1,63 g, 0.0407 mo1) in a stirred solution of 5:3 ethanol-water in 200 sl. Sodium borohydride (1.40 g, 0.0370 mo+) was added to the reaction system. is heated to 55°C. After 16 hours at 55°C, the reaction system was cooled to room temperature and then carefully poured into IICI (500+sl) and then poured into ethyl acetate. Extracted by This ethyl acetate solution was washed with brine and Mg When dried over S Oa and concentrated, the mixture of alcohol heptalactones can be obtained in quantitative amounts. This mixture and P-)luenesulfonic acid (0, 05 g) in 250 ml of benzene is heated under reflux. After 2 hours, the reaction system Cooled to room temperature, diluted with ethyl acetate, filtered, insoluble polymeric material is removed. The filtrate was washed with saturated NaHCOs, then brine, and MgS Dry over O4 and concentrate to give 6.1 g of white solid (approximately 5% purity). 64%) is obtained.

Dry column chromatography (1:2 EtOAc-hexane dissolution If ) and then recrystallized from benzene-hexane to obtain a material with analytical precision. It will be done.

mp 147-149°C; IR (KBr) 5.73, 6.74, 7°76 , 8.41, 9.74, 13. 36 ci+-';'HNMR (60MH z, CDClx), 5.97 (S, 1, CHCOI), 6°39 (S, 1, Art C and -0), 6.8-7.4 (m, 8, Ar-H) .

result of analysis Calculated value as Cl5H1604: C, 70,86; H, 3,96 Actual value: C, 71, 2; H, 4, 0 implementation 1 main Ethyl 1-methyl-I H-dibenzo, iii dioxosine-two-cooked levoxyle root 6-Methyl-2,2'-methylenebisphenol (3.1 g, 0.0145 mo 1), potassium hydroxide (85%, 2.87g, 0.0434mol) and dichloride Isopropyl alcohol 55m of roloacetic acid (1,2*L O, 0145mol) The mixture in 1 is heated under reflux. After 2 hours of reflux, 1.91 g of 85% KOH was added. and 1.2@l of dichloroacetic acid are added and the reaction mixture is refluxed for 4 hours. this The reaction mixture was then cooled, diluted with 150 Hz of HzO, and quenched by addition of concentrated hydrochloric acid. and extracted into ethyl acetate. This ethyl acetate The solution was washed with brine, dried over MgO, and concentrated to give the gum The crude acid is obtained as a yellow-brown solid. An evaporator of this crude acid and concentrated sulfuric acid (0.2ml) 25 ml of Knoll solution is heated under reflux. After 2 hours, the solution was cooled to room temperature. diluted with CHz cog (15a+1) and solid 1'J az Neutralized by addition of COs. This inorganic material is removed by filtration, and the filtrate is depressurized. Distilled below. The resulting residue was taken up in ethyl acetate, water and then bronchion. When washed in line, dried over Mg5O, and concentrated, an amber colored 3.9 g of syrup are obtained. Dry column chromatography (1:4 ethyla When treated with solution H) in cetate-hegisan and recrystallized from cyclohexane, a white Solid products 1. Og is obtained.

mP78-83℃; TR (KBr) 1759, 1205, 1065, 9 80cm-infection; 'HNMR (CDCIs), 1.41 (L, 3, C HzbH,), 2.52 (S, 3, C'fh), 3.69 and 4.45 ( 2d, 2, (AR)! Once for the river), 4.4 (q, 2, CHI CH,) , 5.05 (s, 1, CH), 6.85-7.5 (m, 7, Ar H); Mass spectrum, m/e (M+) 29B.

dog service lambda soil Methyl 2-methyl-12H-diben7Jd 13 dioxosine-6-carboxy Sylate Isopropyl in a three neck round bottom flask equipped with an IR mechanical stirrer and a condenser. 4-methylbis(1-hydroxy-2-phenyl)-methane in 200+ml tool Tan (10.2 g, 48 mmol) and potassium carbonate (26.33 g, 190 mmo1) is placed. Dichloroacetic acid (3.93ml 1.48mmol) was then added. and the mixture is heated under reflux for 1 day. Furthermore, dichloroacetic acid <3.　 93ml (1.49mmol) is added and reflux is carried out for another 3 days. 400 ml of water are added to and the mixture is acidified with hydrochloric acid. Pour this mixture into the chamber After stirring at room temperature for 2 hours and extracting twice with 200 ml of ethyl acetate, the organic layer was collected. Washed with 1M HCHCl20O and 150ml brine, magnesium sulfate dried and filtered. After removing the 78 medium, approximately 17 g of brown oil was obtained. Ru. This oil was dissolved in methanol 1501 and 0.3 ml of concentrated sulfuric acid was added. be done. The mixture is heated under reflux for 2 hours and then cooled to room temperature. carbonic acid Sodium is added and the mixture is stirred for 172 hours. Filter this mixture The solvent was removed, and the trachyhedra were dissolved in methylene chloride and 5% water. Washed with 100ml of sodium oxide and 150+il of brine, MgSO4 dried and filtered.

The solvent is then removed, yielding approximately 7 g of a brown solid. This is ethyl as a solvent. Chromatographed on dry column silica gel using ether/hexane. Approximately 5.5 g of white solid is obtained. This solid is ethyl ether/ Recrystallization in hexane gives 4.51 g of a white solid.

mp 106-108.5’C; Summer R (KBr) 1761, 1748c hi”; HNMR, (CDCl2), 2.27(s, 3H, ctt s), 3,3, 3,5, 4,46 and 4.67 (q, 2H-CH), 3. 92 (S, 3H10CH2), 5.02 (s, IH, CHO), 6. 8 5-7. 5 (m, 7H1 aromatic H).

result of analysis Calculated value as C1tH+i04: C, 71, 82i H, 5, 67 Actual measurement value: C, 71, 5i H, 5, 7 Jyojumasu 25 3-Methyl-L2H-diben・'dL M in dioxane Sodium hydride (5.7 g of a 50% dispersion in oil washed with petroleum ether) 0°1193mo+) and 1,4-geo of 18-crown-6 (0,45g) 1.4- of dichloroacetic acid (4, Owl, 0.049 mol) in suspension in xane 65 ml of dioxane was slowly added dropwise over 15 minutes, and then 1.4- 5-Methyl-2,2' methylene bisphenol (6,3 6 g, 0.0297 mol) are added dropwise over 45 minutes. This anti The reaction mixture was then heated at about 90°C for 18 hours and then refluxed for 4 hours. The mixture was cooled to room temperature, poured into 600 μl of H, and diluted by addition of concentrated hydrochloric acid. Acidified and extracted with ethyl acetate (2X500ml). This Ethylua The acetate extract was washed with brine, dried with MgSO4, concentrated and semi-solid. 9.9 g of a solid crude product is obtained. By cyclohexane extraction in a Soxhlet apparatus Upon purification, the product is a white solid5. 0 (62.3%) is obtained.

mp 149-152℃; IR (KBr) 1730, 1245, 1220 , 1015 cm-';'HNMR (DMSO-da), 2.2 (S , 3, CHI), 3.54 and 4.3 (2d, 2, h +ta+ H+zb), 5.01 (s, ],, Ha), 6.8-7.5 (m, 7, A r-H).

result of analysis Calculation as C+ h H+ -04 4IL: c, 70. 7i H, 5, 3 Actual value: C, 71, Ii H, 5, 22 carboxy=”- Crude 6-methyl 2,2'-methylenebisphenol (7.0 g, 0.0327 mo 1), potassium hydroxide (5.5 g, 0.098 mol) and dichloroacetic acid (2 , 7 ml, 0.0327 mo+) in isopropyl alcohol 1.30a+1 The mixture was heated under reflux for 23 hours, followed by potassium hydroxide (0,0 98 mol) and then dichloroacetic acid 2.7 m+] (0,0327 mo+ ) is added and the reaction mixture is reheated for a further 3 hours under reflux. This mixture was cooled to room temperature, diluted with 400 parts of water, and added with concentrated hydrochloric acid (15 parts per part). Acidified by addition of and extracted with ethyl acetate (200 ml) to obtain I have it! The solution was washed with brine, dried over MgO, and concentrated. Ru. The residue is then azeotroped with toluene to obtain 10 g of crude acid as a brown solid. This coarse A solution of the acid solution and concentrated sulfuric acid (0,6...1) in 100 ml of methanol was heated under reflux for 2 hours. The second reaction was then cooled to room temperature and diluted with 25 ml of CLCI. and neutralized by addition of solid Nag cm5. Inorganic salts are removed by filtration. The filtrate is concentrated under reduced pressure.

This residue was taken up in an ELOAc-ether mixture, water, 5% NaOH in water. solution, then brine, dried over MgS Oa, and a When mixed, 7.0 g of yellow beetroot is obtained. Dry column chromatograph (1: 4. EtOAc-”-Kidun) yielded 4.1 g of product as a white solid ( 44%) is obtained. The purity of this solid was greater than 95%. Is it cyclohexane? Recrystallization gives 2.1 g (23%) of pure product.

mp 107-109? ; IR (KBr) 5.74, 6.97, 8°3, 9 ．． 5, +0.2, 13.5 cr’;’HNMR (90MHz, C1) C1 s), 2.23 (s, 3, CH,), 3.41 (d.

■, H-C and), 3.95 (S, 3, ocHs), 4.62 (d, 1 ．． , HC-H), 5.04 (S, 1, 0 CHO), 6°9-7.4 (m, 7, Ar-H).

result of analysis Calculated value as CI 7 H+ -04: C, 71, 82;) (, ri, Ei 7 real day i: c, 71. 8; H, 5, 6 fruit 1J lion 1 2-methoxyethyl-12H-dibenzo d 13 dioxosine-6-carbo xylate 12H-dibenzo(d,g) (1,3)dioxocin-6-carbonyl chloride ( 5.33 g, 19.5 mmol) was dissolved in toluene and 2-methoxy Ethanol (2,21w1.27.6mmol) and triethylamine 7s+1 Add to toluene solution at 0-10'C under argon. This mixture was refluxed for 3 hours. Heated under flow, cooled to room temperature, poured into water 150++1 and poured into ethyl alcohol. Extracted with 4 x 100 ml of acetate. The obtained organic solution was 5% hydrochloric acid and 5% hydric acid. washed with sodium chloride and brine, dried with magnesium sulfate, and filtered. When the solution is removed, a brown solid is obtained, which is used as a solvent. Chromate on dry column silica gel using thyl ether/hexane (1:1). Matographing gives a yellow oil. This oil solidifies and is solid is filtered and washed with ethyl ether/hexane to give a white solid. It will be done.

mp74-76°C; IR (KBr) +779, 1581 cr’;’H NMR (CDC1,), 3.42 (s, 3H, CH3), 3°3-4.0 ( m, 3H, CH and OCH, 4. 35-4. 8 (m, 3HS CH and OCH,), 5.1 (s, LHl 0CHO), 6, 9-7. 4 5 (m, 8H, aromatic).

result of analysis C+ s H+ m Calculated value as 0%: C, 68, 78; H,! 'l.

77 actual measurement value F C, 69, 1; H, 5, 9 implementation spot 28 2-ethylhexyJIi -12H--,;<7-7'u, -LLL123 'i, $47>y di6--carboxylate 12H-Dibenzo(d,g)C1,,3Edioxocin-〇-Silvonyl chloride 4 g, 0.015 mol) in 45 ml of toluene was added 2-ethylhexyl Sanol (2.28g, 0.017mo+) and triethylamine 4ml solution A toluene solution of O'C under Rougon is added. This mixture was heated under reflux for 2 hours. cooled, washed with 5% NaOH1 then brine, and washed with magnesium sulfate. dried in a vacuum and filtered. When the solvent is removed, a brown liquid is obtained. , which is a dry column silica gel using ethyl ether/hexane as solvent. Chromatography on a column gives a yellow oil (4.5 g).

IR (neat) 1770, 1580 cm-';'HNMR (CDCa t), 0,5 2.0 (m, 15H, CHt and CH,), 3゜33, 3,53, 4.48 and 4.68 (q, 2H, CH□), 4,, H5-4, 35 (d, 2H, OCR,), 5.2 (s, IHlCH), 5. 9 -7. 4 (m, 8H, aromatic).

result of analysis CtsH□0. Calculation as +i: c, 74. 97; H, 7, 66 actual measurement value : C, 75, 1; H, 7, 9 implementation meeting g9 4-t-butyl-2,21-methylenebisphenol (3,67g, 0.0 143 mol), potassium hydroxide (2.85 g of 85%, 0.0429 mol) and isopropifide of dichloroacetic acid (1,1,8+al, 0.0143 mol) A mixture in 55 ml of real alcohol is heated under reflux. Return @ 17 hours later, 85 %KOH1°90g and dichloroacetic acid 1.18a+1 were added and refluxed for 4 hours. It can last for a while. The reaction mixture was then cooled to room temperature and diluted with 150 ml of Hz extracted into ethyl acetate, acidified by addition of concentrated hydrochloric acid, and extracted into ethyl acetate. Ta. The ethyl acetate solution was washed with brine and dried with Mg5Os1. , and upon concentration, the crude acid is obtained as a yellow-brown syrup. This crude acid and and para-toluenesulfonic acid (0.07g) in 10:I CHCl3-ethanol The solution in 25 ml of water is heated under reflux for 1.5 hours with azeotropic transfer of water.

This solution was then cooled to room temperature, diluted with CI (CI x 50+*l, water, Washed with 5% aqueous NaOH, then brine and dried over MgSO= 3.93 g of yellow-brown White Nobu is obtained. Drop this column chromatography (1:4 BtOAC-hexane solution), 2.4 g (49%) of a whitish-gray syrupy product are obtained.

IR (neat) 2975, 1770, 1755, 1485, 141 0, 1260, 76 cm-';'HNMR (CDCl3) 1.24 (S, 9, C(CHs)s), ], 43(t, 3, CH, CH l), 3.43 and 4.51 <2d, 2ARt CHHz), 4.3 9 (q, 2, CH, CH,), 5.05 (s, I CH), 7.0-7.4 (m, 7, Ar-H); 7 soot vector, m/e (M+) 340, (M +-CH5) 323, (M+-CH,CH,0H)294, (M+-C4 HI') 283, (M+ -CO, Et) hydrogenated 1 sum (with petroleum nityl 2.55 g of a 50% dispersion in oil) and 18-crown-6 (0,2 g) in 1,4-dioxane 30-1 was dichloroacetic acid (1,81m+, 0.0219 mol) of 1,4-dioki9730*lff1 solution was added over 15 minutes. dripped slowly. Continue to add 1,4-dioxane'40m+[5-1li Fluoromedyl-2,2″-methylenebis, phenol (3°56g, 0.01 The reaction system into which 33 moles were added dropwise over 45 minutes was heated under reflux for 20 hours, Cooled to room temperature, poured into HtO300+sl and diluted by addition of concentrated hydrochloric acid. Acidified and extracted with ethyl acetate (2X 200ml). this The ethyl acetate extract was washed with brine, dried over Mg5Oa, and It is then concentrated and an oily residue is obtained. This is further washed with petroleum chloride and chill. 4.6 g of an orange-yellow semisolid are obtained. This substance and p-toluenesulfonic acid A solution of (0.07 g) in 30 ml of 10:I CHCl,-ethanol was mixed with water. Reflux and heat for 1 hour with the boiling off. This solution is then cooled to room temperature. diluted with CHCI s 50+*l, H80, 5% N a OH aqueous solution, Washed briefly with brine, dried over MgSOa, and concentrated in the dark. Gives 3.75 g of colored residue. Franche chromatography (1:6 By performing ethyl acetate-hexane elution) a white solid product 1.9 1 g (41%) is obtained.

mp 78-81'C; IR (KBr) 1765, 1325, 1115 , 990 cm-': 'HNMR (CDCl3) 1.41 (t, 3, C , H-z CHi), 3,52 and 4.51 (2d, 2, H-th a, )+1! b), 4.41 (q, 2, CHICtb), 5.09 (s, 1 , H,), 7.0-7.5 (m, 7, Ar-H).

result of analysis Total 'lt value as CI@H15F, 04: C, 61, 37; H, 4, 29 Actual measurement: C, 61,4; H, 4,2 length L fire fire 48 two-part lid j > t, = 12H- dihenzo d 6-carboxylate 2.2'--methylenebis-6-methylphenol (4.0g, 0.0175m o, dichloroacetic acid (1,45ml 1.0.0175mo+) and potassium carbonate (9.7g, 0.070mol of isopropyl alcohol D-Jl/mixture in 100wl) The mixture was heated under reflux with vigorous stirring for 24 hours, then dichloroacetic acid 1, 45 ml are added and the mixture is refluxed for 70 hours with stirring. child of isopropyl alcohol was removed by distillation under atmospheric pressure and at H:0. gradually replaced. The mixture was cooled to 0°C and the solids were removed by filtration. Can be collected. Water (75 ml) was added to the solid and the mixture was dissolved in concentrated hydrochloric acid. becomes strongly acidic. This mixture was extracted into CI□C1 and washed with brine. dried over MgSO4 and concentrated to give 3.0 g of carboxylic acid (73% ) is obtained.

Esterification (methanol, H,S base, reflux) followed by dry column chromatography Matography (performing t8ji with 1:4 ethyl acetate-hexane) This gives 1.9 g (50%) of a white solid product.

mp 134-135°C; IR (KBr) 5.65, 6.72, 8°2, 13.1 cra-';'HNMR (60MHz, CDCl5) 2°21 (s,, 6, 2CL), 3.38 and 4.62 (2d, 2, CHt ) 1.4.0 (s, 3, CH,), 4.99 (S, 1, CH) 6. 9-7. 3 (m, 6, Ar-H).

result of analysis C,,■III! 04 ・1/4 Subtraction value as H, O: C, 71, 4FH, 6,16 Actual measurement +a: c, 71.2; 2.2-methylenebis-6-chlorophenol (10.0g, 0.0372mo dichloroacetic acid (3,07ml 1.0.0372mol) and potassium carbonate ( 20.6g, 0. Mixing in 149 mo of isopropyl alcohol 1501 The mixture was heated under reflux with vigorous stirring for 24 hours, then dichloroacetic acid 3.0 7 ml are added and the mixture is refluxed with stirring for 67 hours. Iso Propyl alcohol is removed by distillation at atmospheric pressure and gradually replaced by water. It will be done. The reaction mixture was cooled, acidified by addition of concentrated hydrochloric acid, and C Extracted with HClz. Chloroform extracts were washed with brine and treated with charcoal. The crude carboxylic acid 12.3 give g.

Esterification (methanol, H, SO=, reflux) and subsequent (dry column) Chromatography (eluting with 1:4 ethyl acetate-hexane) gives a white color. Gives 5.29 g of solid product.

mp 114-116°C; IR (KBr) 5.65, 6.95, 8°29 ,9. 47 10. 3 CI-';'HNMR (60MHz, CDC1, ) 3.47 and 4.67 (2d, 2, CH,'), 3.99 (S, 3, CH,), 5. 04 (s, L CH) 6. 9-7.　3( 8, m, Ar-H).

result of analysis Calculated value as Cl6H1ICl t04: C, 56, 66; H, 3, 5 7 Actual measurement value: C, 56, 7i H, 3, 5 tipped square run 1 3, --9. =-η±, IL/-J, g-U 2 requests △Lmu' 11111 Tsuo Kisoshi Ni Ni Ni Seiko Z Acid 2.2-methylenebis(5-methylphenol) (8.3g, 0.0364m0 1), dichloroacetic acid (3.0 ml, 0.0364 mol) and potassium carbonate ( 20,1,g, 0.145mol of isopropyl alcohol mixed in 220ml The mixture was heated under reflux with vigorous stirring for 24 hours, then dichloroacetic acid 3.　 0 ml (0,0364 rno) was added and the mixture was refluxed for a further 72 hours. be swept away.

Isopropyl alcohol is distilled off and replaced with water. This reaction mixture is First, cool to room temperature and acidify by addition of concentrated hydrochloric acid (35 ml). formed The solids were collected by ilt filtration, taken up in ethyl acetate, and then The ethyl acetate solution was washed with MCI IN, then brine, and Mg dried over SO and concentrated to give a quantitative amount of the crude product as a brown solid. Goods can be obtained.

, the crude product of 2 is extracted with hot chlorohexane in a Socs 1 extractor, and then cooled. 4.55 g (44%) of the product was obtained as a white solid from the cyclo-N xane solution. can get.

..., recrystallization from hexane yields a pure substance with analytical precision.

nip 172-174'C; IR (KBr) 3.4, 5.8, 8.0 ．． 8.91 edition; 'Ht+MR (60Mn2., DMSO-as) 2゜2 1 (3, 6,, 2CH,’l, 3.52 (d, 1, H-C-H) 4.23 (d , 1, H-C-old, 6.8-7.4 (6, ml, I\, -, -Ll'l .

result of analysis C,,H,. jf calculation value as 04 and 7: C,', 1. 82: H, 5 , 67 actual measurement Id 匝: C, 72, t: H, 5, 7 length example -; , / +1L-3, ---3J-2-Z-3j'y--12H-IQ-<) 7n σ-[j-1111, 3-n t4'',)-y, Nuni G-2-cho-1? Sea μ -J-K=Isopropylene potassium hydroxide (1.29g, 23mmol) Pator l in OO+1? 1,1'-methylenebis(4-methoxy-2 -phenol) (1,8 g.

6.9 mmol) was added, followed by 0.6 mmol of dichloroacetic acid. 6ml (7.2mm o l) is added. This mixture is then heated under reflux overnight. was cooled to room temperature and potassium hydroxide (1.29 g, 23 mmol) and Dichloroacetic acid (0,6TI+, 7.2 mmol) is added. This mixture is re- and refluxed overnight. The solvent is removed on a roLavap and the water is added.

The mixture was then acidified with concentrated hydrochloric acid and extracted three times with ethyl acetate-I. It will be done. The organic layer was washed with brine, dried over magnesium sulfate, and filtered. be done. Removal of the solvent leaves a yellow oil. This oil was dissolved in 30@l methanol. and boron trifluoride etherate 1-1 is added. This additive is It was then stirred at room temperature for 4 hours and poured into a saturated aqueous sodium chloride solution (50 ml). , and extracted three times with ethyl acetate. The resulting solution was 5% hydroxylated. Washed with sodium (50 ml) and brine and dried with magnesium sulfate. and filtered. When the catalyst is removed, a yellow oil remains. This oil is a solvent dry column on silica gel using ethyl acetate/hexane (2:1) A white solid (1.16 g) is obtained by chromatography.

mp 102-106’C; IR (KBr) L750, 1620, 15 05 (11'; 'HNMR (CDCI) 3.25, 3.4, 4°31 J, 4.45 (q, 2H1CH,), 367 (s, 6H.

OCH Ri, 3.92 (S, 311, OCH Ri, 5. oecs, 2H, 0 CH) 6. 5-7. 25 (tri, 6H1 Aromachi Tsuku).

result of analysis C + eH + gO, and the tenometer X (a: C, 65, 45; H, 5, 49 actual measurement ( 1: C, 65, 2; H, 5, 5 return 2p West Flame first Su 1 up Sodium hydride (1..65 g of a 50% dispersion in oil washed with petroleum ether, 0.0343 m01 (and 18-crown-6 (0,13 g) of 1,4-dioxa dichloroacetic acid (1,1 A solution of 7 liters (0.0142 mm) was slowly dripped over 15 minutes, and then 6-L-Butyl-2,21-methylene in l,4-dioxane 2+, ml Bisphenol (2.2g, 0.00858mol) was added over 25 minutes. and then dripped. The reaction mixture is then heated under reflux. 24 hours after reflux , the reaction mixture was cooled to room temperature, poured into HrO150at, and concentrated hydrochloric acid ( acidified by the addition of 10+1) and ethyl acetate) (2X100 1) is extracted.

The extract is washed with grains, dried over MgS Os, and concentrated. gives the crude carboxylic acid as a yellow-brown syrupy residue. This thing is ether (]5 Ugly I) and excess ethereal diazomethane (ether 30m Approximately 0.6g of - After standing overnight, the reaction mixture is evaporated and The residue was subjected to dry column chromatography (1:4 with 11.0 AC-hexane). elution) to give 0.66 g of product with slight impurities. pre When treated with parative TLCct: io ether (dissolved in petroleum ether WR) 0.44 g (16%) of pure product is obtained as a gray solid.

mP 113-117”c; TR (KBr) 2950, 1760, 12 05 970 cm-':'HNMR (CDC1,) 1.3 (s, 9 ( CHff)! C), 3.42 and 4.6 (2d, 2, CHz), 3゜94 (S, 3, C00CHs), 5.05 (s, 1, C old, 6, 97- -7. 4 (m, 7, Ar-H).

result of analysis C a. Calculated value as HztOa F C, 73,6; H, 6,79 Actual value: C, 73, 5; H, 7, 0 fell 1 ball - 4-Methyl-12H-dibe ηL℃tun 13 dioxone-sei] 5y salt 4-methyl-! 2H-dibenzo(d,g)(1,3)dioxosine-6-kale Bonic acid (0.64 g, 0.00237 mol) and jetanolamine (0° A solution of 25 g, 0.00237 mol) in 6.4 ml of THF was stirred at room temperature. Ru.

After 18 hours, the clear solution was 1111i! under reduced pressure. and the remaining liquid is ether 1 Stir with 5 liters. This ether is then decanted to produce a clear syrup. remain. This syrup, when dried under reduced pressure, produces a white extractive crystalline form of 0.8 F1 g. (99%) is obtained.

IR (thin film) 3.0, 6.15, 8.12, 10.32;'H NMR (CDCIs) 2.21 (s, 3, CH, 3,4-3,5 (m, 5, 2 CH, and (Ar)t CH), 3.8-4.2 (m, 4, 2 cHz, ), 4.45 (d, 1, (Ar)z-crude 12H-dihenzoCd, g ) (1,3) Dioxosine-6-carboxylic acid chloride (4,3g, 0.016 mol) and triethylamine (3.3 ml, 0°24 mol of toluene 40 Aniline (1.6 ml, 0.017 mo +) in toluene in a stirred solution in +sl The solution in 10-1 was added dropwise over a period of 5 minutes. Stir at room temperature for 4.5 hours Afterwards, when the reaction product was filtered, the generated insoluble matter remained. This filtrate is evaporated under reduced pressure. Retained. The obtained residue was subjected to dry column chromatography (1:2 ethyl alcohol). Purification by elution with acetate-hexane gives 3.2 g of product.

Recrystallization from ethyl acetate-hexane yields 1.8 g of white solid product (35 %) is obtained.

mp 164-165°C; IR (KBr) 6.0, 6,79, 6°97, 8.28, 10.35, 13.27 m;'HNMR (60MHz, CD CIs) 3. 45 and 4.55 (2d, 2, CHt), 5.0 7 (s, L CH), 7.0-8.8 (m, 8, A"-old, 8.6 (b, 1, NH).

result of analysis Calculated value as Cg+H+tCh: C, 76, 1; H, 5, 2i N, 4.　 2 Actual measurement value F C, 76, O; H, 5, 3i N, 4.　3 main examples niza-t2H-dibenzo d13 dioxosine-6-carboxylic acid Sodium hydride (4.93 g of a 50% dispersion in oil washed with petroleum ether, 0 ．． 1 mol) and 18-crown-6 (0.39 g). 4-dioxane 1 of dichloroacetic acid (3.5 ml, 0.04 mol) was added to the suspension in 55-1. ．． A solution of 4-dioxane 55 intestine 1 was added dropwise over a period of 15 minutes and then Continued 3-hydroxy-2-(2'-hydroxybenzyl)pyridine (5,17 g, 0.026 mo+) in 1,4-dioxane 75-1 for 40 minutes. added by dripping. The reaction was then heated to reflux. Reflux 24 hours Afterwards the reaction was cooled to room temperature, poured into water 5001 and added to IN HCl. and extracted with ethyl acetate (3 x 500 ml). It was done. The ether acetate extract was washed with brine and purified over Mg5OJ. Dry and concentrate to give the crude carboxylic acid as a tan solid. meta Recrystallization from nol gave 1.5 g (23%) of pure product as a gray solid. It will be done.

mp 224-227°C (d); IR (KBr) 174B, 1440.1 225,975 tt-';'HNMR (DMSO-d,) D=d 3゜ 8 and 4.55 (2d, 2, Hlfm and H1□k), 5.2 (s, 1, H,), 7.0-7.5 (m, 6, H3, H4, H3, H5, H+ o, I(,), 8.2(m, 1, Hri.

result of analysis C,, H,, NO, ・1/2 calculated value: C, 63, 15; H, 4, 5; N, 5 ．． 3 C, 63,0; H, 4,2; N, 5. 0 Implementability 39 to 11 Other examples of compounds within the scope of this invention are listed in Table A. These compounds are It was manufactured according to the procedure given in the examples described above.

Implementation side 9-8 Depart! Sekibe Ω excluded! activity Indicates herbicidal activity after germination (P r e ) and/or post-emergence (Post). Herbicide swarming tests are performed to distinguish between different compounds. Designated test.

Plants are seeded in separate fibrous stands (8X10X3 inches deep) with pasteurized soil. 1 Hirabayashi for post-emergence is sown 2 weeks before treatment 0 Hirabayashi for pre-emergence is tested The seeds are sown one day before the compound is used. 1 germination unless otherwise specified Pre- and post-emergence Hirabayashi are used to test one compound. test Before the formulation is applied, the pre-emergent Hirabayashi is moistened with fog to stabilize the soil surface. be done. The standard experimental recipe at a treatment rate of 3 kg/h a is for test compound 7 Weigh out 3.61 gg and put it into a 125 ml flask, then add 40 ml of acetone. by adding 0.1% ol)X-77 surfactant. will be produced. If the test compound is not soluble in this formulation, use an ultrasound probe to Processed for 2 minutes.

If it is still not soluble, it should be large enough to pass through the spray nozzle. Grind and reduce particle size. After creating the test formulation, each compound was Using a hand-held spray gun with a handle, spray evenly over the above-mentioned pre-emergent and post-emergent Hirabayashi. Sprayed all at once and completely. The spray gun is filled with acetone while each formulation is used. Rinse with water. The treated Hirabayashi is then transported to a growth room or greenhouse. It is stored here, properly irrigated for 13 days and subsequently processed. Konoto Kihirabayashi has an inhibitory effect (inhibicidin)/inhibition compared to an untreated comparison product (control). When evaluated to determine the system, the evaluation rate number is 0, meaning it is harmless. 100 indicates complete death or control, 80% co Compounds showing control post-emergence and 50% control pre-emergence were further tested. be considered for carrying out the The results are shown in the table below.

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The following examples and tables demonstrate the plant growth regulating activity of the glyoxylate compositions of the present invention. It indicates dryness.

Implementation team 99 Lawn growth effect The acid form of glyoxylate produced in Example 1 was found to be effective in slowing growth in four lawn species. As a spreading agent, the rate of change as shown in Table 2 was evaluated.

Lawn seeds were planted in 8x8cm fiber pots using steam sterilized soil and well Cultivated until growth, for example, until the buds spread to the bottom of the fiber pot. This lawn is It is regularly pruned to keep its height at a manageable level and is The lawn was cut to 1 c- before applying the 6 compounds that had been transported to the lawn to this lawn. It was. The compound is formulated in 15 x 125 m disposable test tubes and is using a DeVilbljss model (BGA-502) handheld sprayer. Autumn leaves were replenished inside the hood.

Height measurements were taken two weeks after compound application and these results are shown in Table 2.

Table 2 *Average value of 2 experiments Some phototoxicity was observed with this method, particularly for Kentucky bluegrass. There is a good delay effect regarding the speed.

Examples ゛゛゛゛　t Using the lawn species described in Example 99, grown similarly, Example 16 The effect of the method of applying the compound of 2 and 2 is evaluated. The results are shown in Table 3.

After 2 weeks, each lawn pot was cut to a certain height and the amount of cuttings from all types were combined, opened and dried before weighing, and their weight was determined.

Table 3 *Average value of 2 experiments Application in granular form provides the lowest phototoxicity results for turf species.

Not implemented 11th Wheat q growth lessons! Wheat is tested in 13c+a round bottom plastic pots. wheat is indigenous 75% soil and 25% steam sterilized to control weed species and pathogens. 0 seeds to be planted in the sand mixture After the seeds are sown, the soil-sand mixture is spread to a thickness of about 10- covered and placed on a fiber mat within the greenhouse. The pot is a bud The bottom is irrigated until moistened with a mist. After budding, only bottom irrigation is performed. be exposed. Growth stages are recorded during processing, and pots are placed in a spray hood for processing. A commonly used compound is placed in a 15X125 tube and transferred to a Dissolved in setone and 12 sl of water. This compound is a handheld devilbilispregun. (model EGA-502) on the leaves. This sprayer is very small It emits fine spray particles, resulting in maximum coverage of the leaves. The operating area pressure is 8408 m/cm” at four different rates for each of the six growth stages. Applicable.

The growth stages are as follows.

■ 1 leaf II 3/4 leaves, some early axillary buds ru Apparent axillary buds on 3/4 leaves and 2/3 leaves■ν 5/6 leaves and 415 leaf axils bud ■　Sword-shaped leaves, inflorescences within the frame.

VI: Boot stage, inflorescences are formed from the culm.

Results (average of all readings) for compounds of Examples 1 and 16 are shown. 4 and 5, respectively.

Table 4 Influence on weight, height, length and breaking strength of grain Book A 10c Weight required to break the segment Number of grain axillary buds, grain weight, straw weight and ``102'' wheat axils One soft red winter wheat growing in the soil in a 4 inch R brass tink bond. (TriLicum aestivum) seedlings were widely sprayed with the compound of Example 15. will be processed. The plant begins to grow axillary buds upon treatment. There is only one seedling at most. There are several axillary buds, but some have two or no axillary buds. The processing is 6 times (but 5 times for 3gm/ha), and many times throughout the research process. Many parameters have been determined, including the number of blades, number of types (seed heads), and and yield are measured. These and other decisions are shown in Table 6. known Since there is no standard product available on the market, the number of the commercially available standard product is not included. (number of leaves) and therefore more variety per plant. High dose 1 (1000 gm/ha) tends to retard axillary buds.

'DAT = Days after processing Note: Grain was pooled for each treatment and weighed 17 days post-harvest (162 DAT). It will be done. The 3 gm/ha treatment was combined into 6 experiments.

Can be used in places where Tensa 4 (Beta vul ar soil) grows There are many places where weed beet, which does not form a natural phase, is infested. These u Eid beets stand out any time of the season, so these weed beets will definitely continue to spread. Weed beat in sugar beet is enough tI4! fl No selective herbicide available, most possible approach to weed beet control Treat flower stalks early by spraying or painting to prevent seed production. That is.

Three greenhouse experiments were conducted for this purpose and the results are shown in Table 7. Te Plants are grown in 5 inch R plastic pots. Treatment is directly on the flower stem It is done by spray atomization. % weight loss is the new increase in growth of surviving flowers It is based on addition. The compound from Example 1 was acetone/water/surfactant 1 Manufactured as an ab formulation. ROLINDUP (registered trademark 1. Monsanto) and A-RF, ST (Elly, registered trademark) are commercially available herbicides and herbicides, respectively. It is a prescription for growth regulators.

Table 7 1 DAT - Days after treatment 2 Indicates the percentage increase.

1 visit to the conducting doctor Two cases of Ka & Tehiki seedlings affected A lively species of Acer 21 Rikaji + tum (Japanese country maple) The seedlings were mixed with the compound of Example 15 and ATRINAL (registered trademark, Dyke Gluck (dl). sprayed off with an aqueous solution of MAAG (commercially available formulation of kegulac). Not yet Bud removal is performed along with treatment control products. All processed items (4 times each Experiments, recorded for 78 days after treatment) are shown in Table 8.

The glyoxylate dose column indicates that there is no excessive effect at the dose tested. This is a wide range.

Table 8 Two of the 14 seedlings entered dormancy after bud removal.

Implementation B Count on Zalea Azalea (Rhododendron sp, cv 'Elsl Lee' ) Artificial pot in a 4-inch round-bottomed plastic pot with one hollowed-out stump ported to the medium. These cuttings are debudded when transplanting. After growth resumes, Spray run-off is carried out on these plants using a hand-held spray unit. Processing is an example 15 with salt and dikegulac, after branch induction and pruning treated with commercially available plant growth regulators to prevent regrowth. Each Table 9 shows the treatment results for five experiments. The number of flower buds was recorded for 122 days after treatment. be done. Glyoxylate treatment results in an increase in the number of florets.

*All plants are debudded when transferred to pots. “Debudded control ” are debudded twice while other plants are being sprayed.

Implementation blaze 06 0 and 100% acetone were used. Three treatment experiments were performed for each compound. conducted and evaluated. Greenhouse for an additional 3 weeks before compound activity is evaluated. Plants were grown within the tank. The results are summarized in Table 10.

Table 10 Ku♂7f-Y-;y(DC:Z　　F　7/<-r　I　h”rc゛Sub These compounds have shown some degree of increased bud breakage and/or in Taraiming beans. Or branching was seen. The activity for most compounds is at 25 ppm. It tended to be larger at 100PP- than at 100PP-. In short, these compounds It is effective as a branching improver in legumes.

On the spot Bouibe... He Ji Pr1vet Hed e Size W Bravent He The effect of compounds on size retention of Japanese privet was evaluated. potted plants The harvested plastic plants are overwintered in a protected cold greenhouse and warmed up in early March. Transferred to the greenhouse until germination and leaf growth are approximately 30 cII in height. It continued for a month. Blivent hedge plants are usually pruned to the desired shape Therefore, 172 of this plant was pruned before chemical treatment. For plants, use a hand-held soubrayer sprayed until runoff. The compound contains 50% water and Tri as surfactant. ton X 100 in a solvent system of 50% acetone containing 0.1% (v/v) It was added at a concentration of 0 pp-. Two pruned plant experiments were conducted for each treatment; Two repeats of the experiment were then performed on unpruned plants. The height of each plant is recorded on the treatment date. Table 11 shows the height of plants after treatment. This shows the net increase in object height.

Table 11 *The average plant height at the time of treatment was 30 cs+.

**The average plant height at the time of treatment was 40 cm.

It was long. In contrast, the plant height of all plants treated with these compounds It remained the same. These compounds are thus suitable for pruned and non-pruned ・Very effective in maintaining plant size for hedge plants .

The planted Green Anshu seedlings are overwintered in a cold greenhouse and released in early March. It was moved to a warm greenhouse. Within a month, the terminal buds began to elongate and grow.

The plants were then sprayed with the compound using a handheld sprayer and washed off. Compound is 50% water, 0.1% (v/v) Trlton, X-100 as surfactant. Two concentrations of 20pp- and 100fIP- in a solvent system of 50% acetone containing It was used in degrees. Four experimental plants were treated for each treatment. The height of each plant is Table 12 shows the height recorded on the day of treatment and compared to the height 28 days after treatment. This shows the net increase in plant height.

Table 12 *Average planting time during treatment of the number 2' of G1-A-SH The height was 34 cm.

Unsprayed control plants with terminal buds removed grew to 18.3 cm. while plants that were not sprayed and debudded grew to 1 lc-. Similarly sprayed with solvent The debudded control plants increased in height by 15c++ and the debudded and Plants that were not sprayed grew 8.5 cm. All tested against this The compound virtually eliminates terminal bud elongation regardless of the concentration of solution applied. It was.

These compounds are therefore used to reduce the vertical growth of this tree species. Therefore, it seems to have excellent uses.

Example 1l1 A katari viewing against the grass bottom for 5 feet Twenty-three compounds were tested for use as lawn control agents. blue grass , CV Baron and Perennial Ryegrass, CV Pei cv Pennr 1ne was planted in late February in a 3-inch square pot. I got it. Grass was grown for 6 weeks before treatment. The glass is then cut and usually When fertilized at a base of , a thick lawn is obtained. Bluegrass immediately before chemical treatment and ryegrass were pruned to a height of 20 m and 15 mn, respectively. 4 different types of experimental pots at two rates, namely 0.5 kg/ha and 2.0 kg/h treated with a. The compound contained 50% acetone and 0.1% (V) as a surfactant. /V) with 50% water containing Triton X-100. slight change The compound was sprayed with 100% acetone containing Trlton X-100. After processing 2 Weekly plant heights were recorded and summarized in Table 13.

Table 13 Effect of compounds on plant height after 14 days treatment of bluegrass and ryegrass sound The average plant height at the time of this treatment was 20.

** Average plant height at the time of treatment was 15--.

For both bluegrass and ryegrass control No. 11, approximately 2 weeks after treatment. A total height of about 130 mm (net growth of 115 m) was grown. Commercial i IS products Limit and Embark 1 ．． The total plant height was reduced to approximately 30-50@II due to the mullets and seeds. . The same plant height reduction potency was observed for many of the compounds tested. Shikarnaga Some compounds had little or no activity. two more species Responsiveness varies similarly among species, with ryegrass growth being particularly low and regular. In short, this class of compounds seemed to be more susceptible to chemical retardation. The retarded activity of It seems that.

international search report t+-1++mAsIIIlca1啼sli@p=T/lI'+. n/Q167 7Pσ/US9010:1672 Vee, Hsrbicidal method claim 2 F1/BB 19067 Inteheb 144, Morris Pill, Pennsylvania 44123 Ohio, Euclid, Lakemon 44060 Ohio, Men Case Avenue

Claims (15)

[Claims] 1. A compound of the following formula in an amount that will effectively control the plants without being lethal to the area where the plants grow. to give something, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Here A is COOR, COSR, CONR'R■, CSNH2, CN, or B -C(=O)O-, R is H, Na, K, di(C1 -C4) Alkylammonium, diethanolammonium, N(3-aminopropylene) lopyl) N-oleylammonium, C1-Cn alkyl, aryl, heteroa Ryl, C2-Cn alkoxyalkyl, C2-C4 hydroxyalkyl, (A alkoxycarbonyl)alkyl, dialkylaminoalkyl, cycloalkyl, tetrahydrofurfuryl or dimethidioxolanylmethyl; R' and R■ are the same or different, each represents H, lower alkyl, cycloalkyl; Kyl, aryl, heteroaryl, heteroalkyl or alkoxycarbonyl is one selected from the group alkyl, or NR'R■ is pyrrolidino, pyrrolidino, peridino, morpholino, piperazino or N-(lower alkyl)-piperazino and Z is H, CH3, CH3S, CH3S(O), COOR, B is H, lower atom alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, (=O) or when used with A is -C(=O)O-, Y is H, C1-C4 alkyl or alkoxy, CF3 or X, and X is F, C1 or Br; Also, if one or more of Y is other than H on any ring, then , these are present in either the 3, 4, 8 and/or 9 position, and Y is on the ring in the 1st, 2nd, 10th or 11th position, one or more of the Y's are other than H. It's not a thing, and one of the Y's is CH3. 2. Contacting a plant location with a compound having the following formula in an amount having a herbicidal effect Methods to control undesirable plant growth, including ▲Mathematical formulas, chemical formulas, tables, etc. ▼ where A is used with one of COOR, COSR, CSNH2, CN, or B. -C(=O)O-, and R is H, Na, K, di(C1-C4) Rukylammonium, diethanolammonium, C1-Cn alkyl, C2- C4 alkoxyalkyl, cyclohexyl, tetrahydrofurfuryl or dimethyl tildioxolanylmethyl, Z is H or CH3, When B is used with H, CH3 or A, it is -C(=〇)O-, and Y is H, C1-C4 alkyl or alkoxy, CF3 or X, and X is F, C1 or Bτ, and where more than one of Y is other than H on any ring, These may be present in any of the 3, 4, 8 and/or 9 positions and if Y is on the ring If in position 1, 2, 10 or 11, one or more of the Y's may be other than H. , and one of Y is CH2. 3. 3. The method of claim 1 or 2, wherein Y, B and Z are all H. 4. 3. The method of claim 1 or 2, wherein B and Z are all H. 5. 3. The method of claim 1 or 2, wherein Y and Z are all H. 6. Y, B and Z at positions 1, 2, 10 and 11 are all H Range 1 or 2 method. 7. Claims 1 to 3, wherein Y and Z are all H, and B is CH2. Or method 2. 8. comprising an agronomically acceptable inert carrier, a surfactant and a compound of the formula: Compositions useful for modifying plant growth, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A is one of COOR, COSR, CONR'R■, CSNH2, CN, or B When used with -C(=O)O-, R is H, Na, K, di( C1-C4) Alkylammonium, diethanolammonium, N(3-ammonium) (propyl) N-oleylammonium, C1-Cn alkyl, aryl, Teroaryl, C2-Cn alkoxyalkyl, C2-C4 hydroxyalkyl , (alkoxycarbonyl)alkyl, dialkylaminoalkyl, cycloal kyl, tetrahydrofurfuryl or dimethidioxolanylmethyl; R' and R■ are the same or different, each represents H, lower alkyl, cycloalkyl; Kyl, aryl, heteroaryl, heteroalkyl, or alkoxycarbonyl or NR'R is selected from the group consisting of pyrrolidino, piperi, such as dino, morpholino, piperazino or N-(lower alkyl)-piperazino represents a saturated monocyclic heterocyclic group, Z is H, CH3, CH3S, CH3S(O), or COOR; B is H; Lower alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, ( =O), or -C(=O)O- when used with A, Y is H, C1-C4 alkyl or alkoxy, CF3 or X, and Beauty X is F, C1 or Br; Also, if one or more of Y is other than H on any ring, then , these are in the 3, 4, 8 and/or 9 position and Y is 1, 2, 1 on the ring If it is in the 0 or 11 position, one or more of the Y's are other than H. There is no, and one of the Y's is CH3. 9. 9. The method of claim 8, wherein Y, B and Z are all H. 10. 9. The method of claim 8, wherein B and Z are all H. 11. 9. The method of claim 8, wherein Y and Z are all H. 12. Claim 8, wherein Y and B are all H, and B is CH3. Method. 13. A patent claim in which B, Z and Y at positions 1, 2, 10 and 11 are all H Range 8 method. 14. A compound having the following formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Here A is COOR, COSR, CONR'R■, CSNH2, CN, or B -C(=O)O-, and R is C2-Cn alco xyalkyl, cycloalkyl, C2-C4 hydroxyalkyl, (alkoxy carbonyl)alkyl, dialkylaminoalkyl, tetrahydrofurfuryl, and dimethyldioxolanylmethyl, and R' and R■ are the same or different. H, lower alkyl, cycloalkyl, aryl, heteroaryl, respectively selected from the group consisting of heteroalkyl, or alkoxycarbonylalkyl or NR'R■ is pyrrolidino, piperidino, morpholino, pipera Refers to saturated monocyclic heterocyclic groups such as dino or N-(lower alkyl)-piperazino. I, Z is H, CH3, CH3S, CH3S(O) or COOR, and B is H, lower alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy , (=O), or -C(=O)O- when used with A, and Y is H, C1-C4 alkyl or alkoxy, CF3 or X, and is F, C1 or Br. 15. A compound having the following formula, ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Here A is COOR, COSR, CONR'R■, CSNH2, CN, or B -C(=O)O-, where R is H, Na, K , di(C1-C4)alkylammonium, N(3-aminopropyl)N-ole Ylammonium, C1-Cn alkyl, aryl, heteroaryl, C2-C n alkoxyalkyl, C2-C4 hydroxyalkyl, (alkoxycarbonyl) ) alkyl, dialkylaminoalkyl, cycloalkyl, tetrahydrofur furyl or dimethidioxolanylmethyl, and R' and R■ are the same or are different, respectively H, lower alkyl, cycloalkyl, aryl, heteroaryl selected from the group consisting of carbonyl, heteroalkyl or alkoxycarbonylalkyl or NR'R■ is pyrrolidino, piperidino, morpholino, Saturated monocyclic heterocyclic groups such as piperazino or N-(lower alkyl)-piperazino and Z is H, CH3, CH3S, CH3S(O), or COOR, B is H, lower alkyl, lower alkoxy, hydroxy, benzyloxy, aceto -C(=O)O- when used with xy, (=O) or A; Y and W are C1-C4 alkyl or alkoxy, or CF3, m and n is 0-2 and the sum of m+n is 1-4.