CA2035024C - Novel glyoxylates and herbicidal and plant growth regulant activity of glyoxylates - Google Patents

Abstract

12H-dibenzo[d,g] [1,3]dioxocin-6-carboxylic acid and certain derivatives thereof (glyoxylates) exhibit plant growth regulant and herbicidal activity when applied to a plant locus.
(see figure I)

Description

NovEL GLYOXYLA'TES AND IIERDIC.IDAL AND PLANT GROWTH
.,~~v REGULANT ACTIVITY OF GLYOXYLATES

BACKGROUND OF THE ItdVEN'fIUN
The invention relates broadly to 1211-dibenzo[d,g] [1,3]dioxocin-G-carboxylic acid and certain derivatives thereof, generally referred to herein as "glyoxylates", and their use as plant growth regulant and/or herbicidal agents and more particularly to their use, usually in combination with appropriate carriers and surfactants, in influencing the growth and development of crops, ornamentals and turt grasses.
Some of the compounds which find utility in the present invention are known generically, and specifically in the case of the methyl ester, from U.S. Patent 3,553,234. Therein, a class of compounds described as 12H-dibenzo[d,g][1,3]dioxocin-G-carboxylic acids and their esters and Having the formula x r --v / ~a ~, r x r wherein X and Y are hydrogen or a halogen and R is hydrogen or lower alkyl are disclosed to have utility as :r:.

1f() 91/8(1(109 fC'1-/US98/83G72 .. _ ?. _ hypolipidemic agents for warm blooded animals. Also mentioned are the pharmaceutically acceptable salts of such acids. An improved class of hyf~olipidemic agents are disclosed by the same inventors in U.S. Patent No.
3,947.,173 wherein ca:rboxamides are also contemplated.
however, no utility in the agricultural field is suggested, and on tests of the specific compounds disclosed in U.S. Patent No. 3,553,234 and U.S. Patent No. 3,941,173 no herbicidal activity was found.
The present invention is based upon the discovery that a selected group of such compounds pos:aesses unexpected activity when employed as plant growth regulant and/or herbicidal agents at controlled dosages, while other closely related compounds within the genus of U.S. Patent 3,553,234 display no significant agrochemical activity.
As used herein, "plant growth regulant" means a compound or composition which affects the maturation and metabolism of plants. hence, a "plant growth regulant" has many effects on plant growth. tfowever, not all plant growth regu:Lant active compounds affect plants the same way. For example, they could affect vegetative growth by retarding or stimulating terminal growth, and/or stimulating side branching and could inhibit new growth such as the developmen t of new sprouts of woody plants, the sprouting of tubers and rhizomes and the development of sucker growth. Such regulants could affect flowering plants by eliminating early flowering, by thinning of blossoms oz- by increasing the number of flowers. Fruit-bearing trees and bushes could be affected by increases in the number, size and quality of the fruit, by producing seedless fruit, by accelerating V'() 91 /1)(10(19 I'Ch/US90/03(r72 .,~ _ senescence and fruit ripening. Doth flowering and fruit plants could be affected by accelerating plant dormancy and maintaining bud dormancy. n "plant growth regulant"
could cause selective postemergent control of weeds by reducing their vigor and competitiveness, and thus prevent their spread and stop normal seeding.
Some specific applications of plant growth regulants include:
preventing lodging of cereals;
increasing production of harvestable tea leaves by promoting side branching;
inhibiting sprouting of potatoes and onions in storage;
suppressing growth of grass, trees, shrubs, and other vegetation in decorative lawn areae~, parks, golf courses and along highways and other rights-of-way;
accelerating fruit ripening and thus, aiding mechanical harvesting by a single or reduced number of pickings;
2U defoliating cotton to permit mechanical harvest;
inhibiting new growth of defoliated cotton and, thus, reducing staining of fiber during mechanical harvesting;
increasing the quality of the hax-vested crop, e.g., sugar content of sugar cane, sugarbeets, grapefruit, grapes, and ottrer fruits;
aiding mechanical harvesting of nut crops by accelerating ripening, stimulating husk cracking and promoting abscission;
protecting crops from drought;

. .
~:
protecting fruit crops from frost by stimulating early dormancy and/or preventing premature breaking of dormancy;
increasing latex flow of rubber;
increasing frost resistance of winter cereals;
reducing the flowering or bolting of lettuce, sugar beets and tobacco;
controlling tobacco suckering;
stimulating increased fruit set of soybeans, peanuts, cotton, tomatoes, melons, and other fruits and enhancing fruit color and quality;
stimulating branching of pot plants; e.g. heather, azalea, chrysanthemum and geranium;
growth retardation in pot plants, e.g. poinsetta, petunia, chrysanthemum and azaleas;
stimulating branching of young fruit trees, e.g. apple and pear.
"Plant growth regulant" also means the retardation of terminal (i.e.
vertical) growth of plants. In grasses and weeds, this regulant activity will retard the grass height and, hence, grass growth. In bushy plants, on the other hand, the resultant retardation of terminal growth by the regulant activity often results in enhancement of lateral growth, an effect desired, e.g. in tomato plants.
SUMMARY OF THE INVENTION
According to an aspect of the invention, a method of inhibiting the growth of undesirable vegetation which comprises contacting said vegetation's locus with a herbicidally effective amount of a compound having the formula C

'A
'~-Z
O
Y.~
wherein:
A is COOR, COSR, CSNH2, CN or, together with one of B, -C(=0)0-;
R is H, Na, K, di(C~ - C4)alkylammonium, diethanolammonium, C~ -C8 alkyl, C2 -C$ alkoxyalkyl, cyclohexyl, tetrahydrofurfuryl or dimethyldioxolanylmethyl;
Z is H or CH3 ;
B is H or, together with A, -C(=0)0--;
Y is H, C~ -C4 alkyl or alkoxy, CF3 or X; and X is F, C1 or Br, provided that where more than one of Y is other than H on either ring they must be in the 3, 4, 8 and/or 9 positions and, where Y is in the 1, 2, 10 or positions on the rings, no more than one of Y is other than H and that one Y
is CH3.
n 1f() 91/llllllllg 1'CI~/US90/03G72 "' -6-20~5024 There has further been found a method of controlling the growth of undesired vegetation, which method comprises applying to the vegetation locus, especially by postemerc~er~t: application, a herbicidally effective amount of a compound having the same formula as above.
There has still further been found a composition of matter useful in the regulation of plant growth and development, which composition comprises a compound having the same formula as above, an inert carrier and a surfactant.
In one preferred embodiment of the foregoing methods and composition of.- the present invention, Y, B
and Z are all Ii, resulting in a compound having the formula /~o a In a furtl~ri- embodiment of the foregoing mettrods and composition of ttie present invention, B and Z are all Ii, resulting in a compound having the formula Y
~ 10 r--A
~O
m Y

1f() 91/0(1009 I'C1~/US911/03fi72 .-. _7-In yet another embodiment of the foregoing methods and composit:l.ons, Y and Z are all H, resulting in a compound having the formula /--o a The invention also encompasses certain novel compounds having herbicidal and/or plant growth regulating activity having the formula ~Y~
.~ a A
~' ~ z ''' ~ r.
wherein:
A is COOK, COSR, CONK' R" , CSNIIZ, CN or, together with one of B, -C(=0)0-;
R is CZ - C'8 alkoxyal.kyl, cycloalkyl, Cz - C4 hydroxyalkyl, (alkoxycarbonyl.)alkyl, dialkylaminoalkyl, tetrahydrofurfuryl and dimethyldioxolanylmethyl ;

wo mnooo<~ rcriuS~oio3t,~2 R' and R" tnay be the same or different, and each is a member selected from the group consisting of ti, lower alkyl, cycloalkyl, aryl, heteroaryl, heteroalkyl, or alkoxycarbonylalkyl.; or NR'R" taken together represent a saturated monocylic heterocyclic group such as pyyrolidino, piperidino, morpholino, piperazino or N-(lower alkyl)-piperazino;
Z is H, CFi3, CIi3S, C~i3S (O) or COOR;
B is II, lower alkyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, (=O), or, together with A, -C(=O)O-;
Y is H, C~ - C4 alkyl or alkoxy, CF3 or X; and X is F, C1 or Br;
provided that where more than one of Y is other than Fi on either ring they mu~~t be in the 3, 4, f3 and/or 9 positions and, where Y is in the 1, 2, l0 or 11 positions on the rings, no mora than one of Y is other than H. In other embodiments, no more than one of Y is other than FI
on either ring.
Another group of novel compounds within the scope of the invention has the formula 'Y"
~O
A
Z

WherC,'lIl:

~f() 91 /(IU11(19 I'C.'1~/US90/03(72 A is COOK, COSR, CONR'R", CSNHZ, CN or, together with one of B, -C(=0)O-;
R is Ii, Na, K, di (C~ - C4) alkylammonium, N(3 amino-propyl)N-oleylarnmonium, C~ - C8 alkyl, aryl, heteroaryl, CZ - Ca alkoxyalkyl, Cz - C4 hydroxyalkyl, (alkoxycarbonyl)alkyl., dialkylaminoalkyl, cycloalkyl, tetrahydrofurfuryl oz- dimethydioxolanylmethyl ;
R' and R" may be the same or different, and each is a member selected from floe group consisting of 11, lU lower alkyl, cycloalkyl, aryl, heteroaryl, heteroalkyl, or alkoxycarbonylal.kyl; or NR'R" taken together represent a saturated monocyli_c heterocyclic group such as pyyrolidino, piperidino, morpholino, piperazino or N-(lower alkyl)-piperazino;
1' Z iS Ii, CI(3, CIi3S, CI13S (O) , COOR;
B is Ii, lower ~7.kyl, lower alkoxy, hydroxy, benzyloxy, acetoxy, (-O), or, together with 11, -C(=0)0-;
Y and W are C~ - C4 alkyl or alkoxy or CF3;
m and n are o-2 and the sum of m plus n is 1-4.
2o By way of illustration, and not by way of limitation, the following are moieties suitable for use as 11, Z, B and Y in the compositions of the present invention.
As examples of moieties suitable for use as A
25 mention may be made of a carboxyl group (-COOFi), simple esters such as:

COOCIiZCH3 COOCH2CHzCII~

3 0 COOCIi ( CI(3 ) 2 COOCIIZCIiZCIizCII3 COOC ( Cli3 ) 3 l1'() ~) I /11()009 I'CI'/US9f1/03(>72 '"~.. -10 - ' COOCIIZ ( Cfiz ) bCH3 COOCHzCH ( CIIZCH3 ) CIiZCH2CIiZCH3 ~ ~ 3 5 0 2 4 COOC6H>
COOC6Ii5 substituted esters such as:
COOCHZCHZOCIi3 COOCHZCIizOCIizCiizCIizClI3 COOCHZCIi (01i) CIIZOII
O O
1 o coocIIZcIi-cliz COOCHZ
O
COOCH ( CII3 ) COOCIiZCII3 COO CIiZCii2N ( CI I3 ) 2 COOCHzCIi2N ( CII3 ) Z . iiCl amides such as:
CONHZ
CONIiCH3 COIiNC6H5 2 0 CON ( CH3 ) Z
salts such as:
COONa COOK
COON . ( CI I3 ) 21JI i 2 5 coon . ( IiOCIi2ct12 ) zNII
COOII. CII3 (CIiz) ~CIi=CIi (CI12) aNIiCIizCIi2CIizNII2 and other moieties such as:
CI I20Fi CIizOSO2C61-i6-CII3-4 30 CH (OIi) CN
CIi=CIiCOOCIiZCli3 wc~ <mnuouv rctvusooin3~~~z CN
C (=S ) Nfiz C (=O) SCHZCFF3 2 0 3 5 0 2 4 C (=O) NHNHZ.
Z may be:
FF

CIi3S (O) C (=O) OCH2CII3;
F3 may be:
Ii ( CFi3 ) 2 CHZ=

( CH3 ) ZCH-C6H5-CIi20-CIi3C (=O) O-=O
2 5 -CHz-O
( CH3 ) ZCHCOC ( =O ) -lactone (B -+- A) ; and Y may be:
H

Vii'( ) ') I /(IU11119 ( cli3 ) 3c r I'C: f/US9(1/(13072 cl Ii0 CIi30 2 0 3 5 0 2 4 C6Ii5CIiZ0 CIi3C (=O) O
NOz a nitrogen ring structure such as pyridine derivatives.
These and other aspects of the invention will become clear to ote ski.ll.ed in the art from the specification and claims that follow.
DL_I_nII~EU I~F~.SCFtIPTIO_N
When used in the present invention, the terms "plant growth regulant" or "plant growth regulating effect" refer to the ability of a glyoxylate, when applied to a plant locus, to influence the growth and development of useful crops, ornamentals and turf as far example described by illustration hereinbefore. A
variety of effects may be obtained depending upon, among other considerations, the plant in question, the glyoxylate selected and the manner., amount and timing of application. Generwally the result obtained by application of a glyoxylate is the desirable promotion, inhibition and/or alteratian of a plant's physiological or morphological processes, such as accelerating or retarding leaf, shoot and root growth, reduction in stature, increased branching, tillering, terminal inhibition, inhibition of regrowth after pruning thereby 1V() 91 /1)(1(1(19 I'C f/US90103G72 reducing the need for follow-up pruning, increased root growth, delayed budding, increased bud count, yield increases, etc. In particular, the glyoxylates of the present invention have been found to be effective growth retardants when applied to turf grasses such as, perennial rye, red and tall fescue and Kentucky bluegrass. A further example of a plant growth regulating effect is the ability of a glyoxylate compound, when timely applied (preferably in the second or third growth stage) to act as a straw shortening agent on wheat, an especially useful effect where high nutrient levels are employed to increase grain yield.
The use of tyre tei-rns "herbicide" or "herbicidal effect" refers to the application of a glyoxylate compound to kill, or at least substantially inhibit the growth of, an undesired plant. Especially significant examples are the use of one of the glyoxylates to control the growth of weeds, including grassy weeds, in wheat and reduce flowering in bolting weed beets. The glyoxylates have been found to be particularly useful in controlling the growth of the generally hard to control sedges, especially yellow nut sedge, when applied to the soil in which the nut sedge tubers are beginning to germinate.
The compounds useful herein are those having the formula .Y, p A
Q Z
Y~

-. -14-Each of the defined glyoxylate°compounds has been found to have a herbicidal'and,~or plant growth regulating effect. In. addition to activity and selectivity considerations, a particular ester orv salt form of a glyoxylate will often wbe chosen for its convenience of handling and applicatiTon, an example being the choice of the n-butyl ester, which has~~reduced volatility, over the methyl ester form: On the other hand, where volatility is desirable, e.g., for to application by fumigation (smoke bombs) in a greenhouse to induce branching of ornamentals, compounds such as the nitrile and lower esters (e.g. , methyl, ethyl and prQpyl) which are more volatile, may be preferred.
The choice of substituents to=be placed on the benzene rings, on the other hand, seems 'to affect the nature and extent of plant growth regulating effect to be obtained and such substitution is limited with respect to (1) the identity -of the substituent=(2~~ location on the ring or rings and (3).. number of substitutions that may be accommodated. Substitution opportunities are particularly limited when placed in the l, 2, 10 and 11 positions according to the following number system:

~O

O

i ,.., , ... n..~.

11'() ~ll/(111(llly 1'(.'1~/tl5')(1/1).1G71 '.

In such cases, rubstit:utiott of ~ methyl group at no more than one position has been found possible without <a significant loss of lterbi.cidal activity.
5ubstituent possibilities at the remaining benzene ring positions (3, 4, E3 and 9) , i.tt order to vary the growth regulating and/or lm-~rlric.Ldal effect obtained without:
significant overall loss of activity, are more numerous.
Witi_le it i.s preferred tatot_ trot more than one position ort either ring be subs~.:itut.c~cl, the cltoic:e of substituents may be increased as def.ittect 7bove.
Generally the d:lyoxy.lattos wil_1. he applied to the plant locus as the active ittdredient irt a composition also cotnl~rising a carrier. and .~ surfact:ant, that is, a dispersing, emulsify:ittg or wetting agent, although dil.uents, extenders rtnd outer active i.ngredi.ents having a differing or cotnp.l.eumntt:ttt:~y uti.lit:y may be present. The compositions may thus be in ttte form of finely divided particulate solids, gr.attuletx, wettable powders, solutions and dispersions.
i'he inert canri.or may be solid (e.g. , clays, natural or synthetic silicates, talc;) or. :liciui.d (e.g. , water, alcoltols, esters, ar.omati.c hydrocarbons, petroleum fraction;) . 'fhe surface active aqertt:s may be anionic, cationic: or non-i.otic (e.g, , salts of lignosulfonic acids, alkyl-aryl sulfonic acids, acetates of alkylamines attd condettsates of et lty.lmte oxide with fatty alcoltols ou acids) . In addition, tltc~ compositions may contain thickeners, adttes.ivc»;, rt:alt.i.l i_zers, preservatives and other ad juvants known to the art.
Tlte glyoxy.l ates may be applied by conventional tecltniciues (e.g. , slotvead.i.ng, dusting or ~:laz-ayirtg or via -1s- 203502 4 fumigation smoke bombs in confined areas such as greenhouses) in a variety of forms (e.g. , solutions, suspensions, wettable powders or granules).
The compositions of the present invention generally will contain from 5 to 95 percent by weight of the active glyoxylate compound and will be applied at a rate of from 0.5 to 4 kilograms per hectare, when used as herbicides.
While in a plant growth regulating composition the amount of active ingredient may be comparable, the amount employed will vary greatly depending upon the particular glyoxylate chosen and the effect in question, generally ranging from 0.01 gram to 4 kg per hectare. Conveniently, such applications are obtained by spraying a solution containing from 0.1 to 500 ppm active ingredient to run-off, depending on the plant species to be treated.
Some of the compounds which are the subject of the present invention are derived from the acid form which may be prepared by methods known to the art, for example, according to the teachings of U.S. Patent 3,836,543.
Modifications and variations of these procedures where benzene ring substituents are other than those described in the '543 patent and where substitution is desired at the 12 position, are shown in the examples below.
Thereafter they may be converted to the final form generally according to methods also known in the art, for example, conventional esterification when preparing a lower alkyl ester.
In order that those skilled in the art may more readily understand the present invention and certain WU 91/(IOIIU9 1'Cl'/US90/03G72 preferred embodiments by which it may be carried into effect, the following specific examples are afforded.
PREflIRATIONS
l2ti-Dibenzo f d a 1 f ~ 3 1 diox_ocin~6= carboxyl is ac~.d Into a 1?. liter 3-neck flask fitted with an air-driven overhead stirrer and a condenser are placed 2,2'-methylene bisphenol (200.24 gram, 1.0 mol), 4 liter of isopropyl alcohol and then potassium carbonate (552.84 gram, 4.o mol), while stirring. Dichloroacetic acid, (82.5 ml, 1.0 mol) is added over a period of 2 minutes.
During tire addition of the dichloroacetic acid some effervescence is observed. The reaction mixture, which is a white, easily stirred, heterogenous mixture, is heated at reflex and stirred vigorously. lifter 24 hours, the reaction mixture is cooled to room temperature and an additional 82.5 ml (.1.0 mol) of dichloroacetic acid is added. Again, some effervescence is observed. The reaction mixture is then heated at reflex fox an additional 72 hours. 'Total reflex time is 96 hours.
After 48 hours of total reflex time, the reaction mixture thickens and vigorour3 stirring is maintained.
Once the 96 hour reflex period is complete, the condenser is replaced with a distillation head and 200 ml of isopropyl alcohol is distilled off at atmospheric pressure and replaced with 200 ml of H2o. This is repeated until they distillation temperat~.ire reaches 95-100'C. During the distillation procedure, once H2o is 1f!) 91/(Ifll)U9 I'C'F~/US90/03C72 "" -18-added, the reaction mixture becomes much more fluid and eventually a reddish brown homogenous solution is obtained. After the distillation temperature reaches 95-100°C, the reaction mixture is cooled to room temperature. Upon cooling, solids form, therefore it is important to maintain vigorous stirring. The reaction mixture is then made' strongly acidic by the careful addition of concentrated FIC1 (800 ml) over a period of 1-2 hours. Extreme caution must be taken during the addition of the FiCl because of effervescence. The effervescence is particularly vigorous during the latter stage of FiCl addition. Once tl~e IiCl has been added, the reaction is stirred an additional 2 loours at room temperature. The so7..ids are collected by filtration and washed well with FFzO.
These solid: are then placed in a separatory funnel with 2 liters of ethyl acetate and 2 liters of ltd HC1 and shaken vigorously. The organic layer is separated, washed with brine, dried over. MgSO4 and concentrated. The so:Lids obtained are then dried in a vacuum oven to afford 239 grams (93 percent) of crude product as a brown-tarr solid, which are them placed in a Soxhlet extraction aploarat:us and exhaustively extracted with refluxing cyclolrexane (2 liters). Periodically the cyclohexane solution is cooled and the precipitated product collected by filtration. The rate of the extraction depends on how vigorously the cyclohexane refluxes and recycles. There is obtained 147 grams of l2Fi-dibenzo[d,g][1,3]dioxocin-6-carboxylic acid as a white solid: mp 153-157°C; IR (KF3r) 5.78, G.76, 6.93, 8.12, 10.1, 13.1 cm~~; rFi NMR (60 MFFz, DMSO-db) 3.64 and 4.38 (2d, 2, CHZ) , 5.U9 (s, 1, CFi) , 6.9-7.6 (m, 8, ~'~'() 91/fl()11I)9 fC7'/US911/(?3fi72 Ar-Ii); greater than 99 percent purity as determined by liquid chromatography.
~F3utv1 12H-Dibenzo f cl~g~]._~~~ 1 dioxocin-6-carboxvlate Into a 500 rnl round bottom flask flitted with a stir bar and a Dean-Stark apparatus is placed 111.4 grams of crude (87 percent) 1.211-dibenzo[d, g~ [ 1., 3 ]dioxocin-6-carboxylic acid i.n 300 ml of 2:1 n-butanol:toluene. The mixture is stirred at room temperature for 15 minutes to l0 effect the complete dassoltrtion of the acid.
COr7Ce11trated sulfuric acid (4.0 ml) is then added and the reaction mixture is heated to reflux. Immediately upon attaining reflux, an aqueous layer begin s to separate out in the Dean-Stark apparatu s. After 2 hours at reflux, no additional water formation is observed and the reaction is cooled to room temperat=ure with a cold water bath. A
total of 10 ml of water is collected, the majority of this water being formed i.n the initial. 30 minutes of reflux. The cooled reddish-yellow reaction solution is diluted with 200 ml of toluene, washed with 300 ml of water, 300 ml of saturated aqueous NaIIC03, 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 again is concentrated under reduced pressure. This evaporation with toluene facilitates the removal of n-butanol. The residue obtained :is taken up into 300 ml of 2:1 toluene:ether and washed with 200 ml of 5 percent NaOIi. I)rine, 50 ml, is added to break up the emulsion that forms with the 5 percent NaOIi wash.

1V() 9(/()(1009 I'Cl~/I.ISyp/U3fi72 ,..- - 2 0 -The organic solution is then washed with 200 ml of brine, dried over MgSO4 and concentrated under reduced pressure to afford a thick light reddish-yellow liquid (130 grams). This liquid i.s then subjected to vacuum distillation, using a Claisen adapter as the distillation head and an oil bath for heating. Care is taken during the course of the distillation to avoid solidification of the product in the distillation condenser. 11 fore run ( 11 grams) is collected !raving a b.p. 70°C to 17U°C at 0.25 mm. Pure n-butyl ester, 84.3 grams (62 percent) , is then collected from 171 ° C t:o 1FI0 ° C at 0. 25 mm as a thick clear liquid which readily solidifies on cooling to afford a white solid: mp 63-66"C (softening at 60°C); greater than 99 percent purity as determined by L.C. by 189-195'C/0.4mm; IR (neat) 3.45, 5.75, 6.95, 8.35, 10.4 cm-r; H NRM (60 MIIz, CDC13) 0.9-1.9 (m, 7, OCHZCHZCIIZCII3 ) , 3 . 4 2 and 4 . G ( 2 d , 2 , CIi2 ) , 4 . 3 5 , ( t , 2 , OCIi2CIi2CIi2CFi3) , 5.05 (s, 1, CH) , 7.0-7.4 (m, 8, Ar-H) ) .
Anal. Calcd. for Cr91I2o04: C, 73.06; II, 6.45 Found: C, 73.0; Ii, 6.7 Ethyl l2fi-Dibenzofd glf~.3lc~ioxocin-6-carboxylate A solution of 1211-dibenzo[d,g] [1,3)dioxocin-6-carboxylic acid (31.8 grams, 0.124 mol) and conc. HzSOi (1.6 ml) in 215 ml of ethanol is hreated at reflux, allowing the condensate to pass through 4A molecular we ~ o i iuuoo~~ re-w usgoio3~,~2 _21-sieves. After ?. hours, the reaction is cooled to room temperature and 100 ml of methylene chloride is added and then neutralized by the addition of solid Na2C03. The salts are removed by filtration and the filtrate concentrated. The residue is taken up into CH2Clz, washed with water, 5 percent aq. NaOIi and brine, dried over MgS04 and concentrated to afford 31.1 grams (88 percent) of product as a white solid: mp 86.5-88.5'C; IR
(KBr) 5. G3, 6.7, 6.88, 7.2, 8.12, 8.98, 9.25, 10.1 cm-~;
~H NMR (6U MHz, CDC13) 1.4 (t, 3, CII3) , 3.43 and 4.6 (2d, 2, CHZ) , 4.42. (q, ?., C~i2CH3) , 5. 1 (s, 1, CH) , 7.0-7.4 (m, 8, Ar-Ii) .
Anal. Calcd. for C»II~604: C, 71.82; I1, 5.67 Found: C, 71.7; H, 5.8 Methyl l2li-Dibenzo d~l~ 3.] d~lo~tocin-6-carboxylate Preparation proceeds as described in Example 3, only substituting methanol for ethanol. Obtained is a white solid: mp 10'7-11.0'C; IR (KBr) 5.69, 6.77, 8.2, 9.3, 10.05 cm~~; ~Ii NMR (60 MIIz, CDC13) 3.5 and 4.62 (2d, 2, CIIZ) , 3.98 (s, 3, CIi3) , 5.1 (s, 1, CIi) , 7.0-7.5 (m, 8, Ar-H) .
Anal. Calcd. for C~6H~404: C, 71.10; Ii, 5.22 Found: C, 71.0; H, 5.1 1f()') I /11011(1') i'CI~/US90/03C72 J.~_XAM F? LE 5 2 0 3 5 0 2 4 n-Pro>'Y1 12H-Dibenzo d,al(1,31dioxocin-6-carboxylate Preparation proceeds as in Example 3, only substituting a like quantity of n-propanol for the ethanol, to obtain a white solid: (KBr) mp 82-85"C;
IR

5.7, 8.35, 9.4, 10.15 cm~~; ~Ii NMR 0 Mliz, CDC13) 1.05 (6 (t, 3, CIi3) , 1.95 (m, 2, CiiZ~lizCli3)3.47 and 4.65 (2d, , 2, Cliz) , 4.33 (t, CHZC iizCIi3) , 1, CH) , 6.9-7.5 5.1 (s, (m, 8, Ar-H).

Anal. Calcd. for C~BI(~~U4: C, 72.47; ii, 6.08 Found: C, 72.7; 1i, 6.0 EXIIMPT~E 6 iso-I'robyl 12H-Dibenzofd alf~ 31d o oc'n-6-carboxylate The subj ect product is prepared as described in Example 3 , only subsi:it~uting iso-propanol for ethanol , yielding a white solid: mp 94-97'C; IR (KBr) 5.73, 6.78, 8.25, 9.05, 9.4, 10.1 cm~~; ~Ii PJMR (60 MII2, CDC13) 1.4 (d, 6, CH-(CH3)Z) , 3.46 a«d 4.6 (2d, 2, CHz) , 5.03 (s, 1, 0-CIi-0) , 5.25 (m, 1, Cf_1(CII3)Z) , 6.9-7.5 (m, 8, Ar-H) .
Anal. Calcd. for C~BII»04: C, 72.47; Ii, 6.U8 Found: C, 72. 4 ; II, 5. 9 CVO ~) 1 /fIU()09 1'L I'/ US90/03G72 - -z3-t-Butvl l2li-Dibenzo [~q7 [ 1 , '~ l~c i ~xocin-6-ca~~oxylate A solution of 12II-dibenzo[d,g][1,3]dioxocin-6-carboxyli.c acid (3.0 g, 0.0117 mol) in 45 ml of thionyl chloride is heated at reflux. After. 4 hours at reflux, the excess thionyl. chloride is distilled off at atmospheric pressure and then under vacuum to remove traces of thivnyl chloride. The acid chloride obtained is dissolved in 35 ml of toluene and added dropwise over a period of 20 minutE~s to a solution of t-butyl alcohol ( 15 ml ) containing N, N-dimethylanil ine ( 1 . 8 ml , 0.01405 mol). After stirring 23 hours at room temperature, the reaction mixture is concentrated under reduced pressure and floe re ~idue obtained is taken up into ethyl acetate, washed with water and brine, dried over MgS04 and concentrated to yield 3.4 g of a syrupy residue. Dry column chromatography (elution with 1:4 ethyl acetate-hexanes) afforded 1..57 g (43 percent) of product as a white solid: mp 94-97°C; I:R (KBr) 5.75, 8.22, f3.7, 9.43, 1Ø22, 13.21 cm-r; ~Ii Nr'IR
(G0 Mliz, CDC13) 1.6 (s, 9, C(CI-I3)3) , 3.45 and 4.6 (2d, 2, CHZ) , 4.93 (s, 1, CH) 6.95-7.4 (m, 8, Ar-Ii) .
Anal. Calcd. for Cr9HZ004: C, 73.06; II, 6.45 Pound: C, 73.0; Ii, 6.3 1V() 91/110(!09 I'CT/US90/I?3672 .-.
~XhM LE 8 n-Octvl 12H-Dibe o djg,]_["~, ~ l~ioxocin-6-carkJOxylate 12H-Dibenzo[d,g][1,3]dioxocin-6-carboxylic acid (4.o g, 0.0156 mol) anc:i 45 ml of thionyl chloride are refluxed/distilled as i.n Example 7. The acid chloride is then dissolved in 5o ml of toluene and added dropwise over a period of 10 minutes to a soJ.ution of n-octyl alcohol (20 ml) containing triethylamine (2.0 ml, 0.0187 mol). After stirring 20 luours at room temperature, the insolubles that form are filtered off and the filtrate concentrated under reduced pressure.
The residue obtained is taken up into CIiCl3, washed with HZO then brine, dried over MgS04 and concentrated. The residue obtained is purified by dry column chromatography (elution with 1:10 ether-petroleum ether) to afford 4.18 g (73 percent) of product as a clear syrup; IR
(neat) 3.42, 5.63, 6.71, 6.87, 8.95, 10.1 cm~~; tIi NMR
(6U Mliz, CDC13) 0.9-2.0 (m, 15, OCIiZ (Cliz)6(CH3) ) , 3.48 and 4.62 (2d, 2, CIi2) , 4.35 (t, 3, OCIiZ (CItZ)6CH3) ) , 5.07 (s, 1, cH) , 7. 0-7.5 (m, e, Ar-II) .
Anal. Calcd. for C23II7804: C, 74.97; II, 7.66 Found: C, 74.6; H, 8.2 1V() 91/11011119 PC1~/tJS9f1/(?3672 -~- - 2 5 -2 0 3 5 0 2 4 ~X~1MPL~ 9 n-Butoxvethyl l2ti-Dibe~zofd.ctl f ~., 3ldioxocin-~-~~xbo~~.z to Crudel2H-d:ibenzo[d, g][1,3]dioxocin-6-carbonyl chloride (4.8 g, 17.5 mmol.) is dissolved in toluene and treated with a solution of 2-butoxyethanol (2.77 ml, 21 mmol) and 5 ml of triethylamine in toluene at 0°C
under argon. The mixture is heated at reflux for 2 hours and then cooled to room temperature. The mixture is poured into 150 ml of water and extracted with 4 x 100 ml of ethyl acetate. 'fhe organic solution is washed with 5 percent hydrochloric acid, 5 percent sodium hydroxide and then brine, dried with magnesium sulfate and filtered.
The solvent is removed to leave a yellow liquid which is chrornatographed on dry column silica gel, using ethyl ether/hexane ( 1: 2 ) as the solvent, to give a yellowish oil (4.3 g, 69 percent). An analytically pure material is obtained by using F~reap tlo.in layer chromatography. IR
(neat) 1770, 1582 cm's. Eli NMIZ (CDC1.3) 0.75-1.3 (m, 31i, Clip) , 1.2-2. 0 (m, 41f, CIIz) , 3. 3-4. 0 (m, 5N, OCHZ and benzylic) , 4 .4-4.9 (m, 311, OCOCIIZ and benzylic) , 5. 6 (s, 1H, Cli) , 6.9-7.5 (m, 81i, aromatic) .
Anal. Ca~.cd. for CZ~Hz,~05: C, 70.7; H, 6.79 Found : C, 7 0 . 4 ; li , 6 . 9 1f() 91/IIUOtl9 I'Cf/1JS90/03672 ,~- -26_ ~XAj~]PLE 10 Cvclohexyl 12H-Dibenzord.qlLl,3~ dioxocin-6-carboxylate Crudel2li-dibenzo[d,g][1,3]dioxocin-6-carbonyl chloride (4 g, 14.5 mmol) is dissolved in 45 ml of toluene and treated with cyelohexanol ( 1. 75 g, 17 . 5 mmol ) and 3 ml of triethylami.ne at 0°C under argon. The mixture is heated at reflux for ?. hours, cooled, washed with 5 percent sodium hydroxide then brine, dried with magnesium sulfate and filtered. 'fhe solvent is removed to leave a brown liquid which is chromatographed on dry column silica gel, using ethyl ether/hexane as solvent, to isolate a yellow :solid. This solid is ~aecolorized with charcoal to give a off-wtrite solid (4.32 g, 87.7 percent) , mp 120-125'C: IR (KiSr) 1755, 1.580 cm~~. ~Ii NMR (CUC13) 1.0-2.4 (m, 11II, cyclohexyl) , 3.37, 3.6, 4.51 and 4 .73 (q, 2I(, CIIZ) , 5.05 (s, III, UCIi) 6.9-7.45 (m, BIi, aromatic) .
Anal . Calcd. for CZ~Ii2z04: C, 74 . 54 ; II, 6. 55 Found: C, 74 . 3 ; ~i, 6 . 6 2 0 EXAMPLE 7.1 Tetrahydrofurfuryl 12II-Uibenzo[d,g][1,3]dioxocin-6-carboxylate _ To a solution of crude l2li-dibenzo[d,g] [1,3]
dioxocin-6-carbonyl chloride (4.25 g, 15 mmol) in toluene is slowly added a solution of tetrahydrofurfuryl alcohol 1f() 91/(100119 I'CT/US90/03C7Z

(. 8 ml, 18 mmol) and 7 ml of triethylamine in toluene at U . under nitrogen. The mixture is heated at reflux for 1 hour, cooled and treated with water and ethyl acetate.
The organic layer is wa:~iied with 10 percent sodium hydroxide then brine, dried with magnesium sulfate and filtered. The solvent is removed leaving a yellowish oil which is chromatograph nd on dry column silica gel using ethyl acetate/hexane as the solvent. The resultant (still yellow) oil i~~ decolorized with charcoal and solidified to yield a white solid (4.12 g, 78 percent) mp 83-85°C: IR (KF3r) 1760, 1580, cm-~, ~Ii NMR
(CDC13) 1.6-2.4 (m, 4Fi, CII?) , 3.35, 3.57, 4. 5 and 4.71 (q, 2H, CI(z) , 3.7-4. 1 (m, 2.Ii, CIIzO) , 4 . 1-4 . 5 (m, 31'i OCHZCIIO) , 5. 1 (S, lII, CII) 6. 95-7.5 (m, BII, aromatic) .
Anal. Calcd. for CZONzoOS: C, 70.58; Ii, 5.9?.
Found: C, 70.8; II, 5.9 EXA1~PLE 12 Ethyl 12H-Dibenzofd c~l_L1~31dioxocin-6-thiocarboxylate 'fo a solution of l2li-dibenzv[d,g](1,3]dioxocin -6-carboxylic acid (1 gram, 3.9 mmol) and ethanethiol ( 0 . 8 ml , 5 . 9 mmol ) in 10 ml of dry tetrahydrofuran at -25'C, is added dicyclohexyl carboximide (DCC, 2 grams, 9.8 mmol) under argon. The mixture is stirred at -20'C
for 2 hours and then kept in ttoe refrigerator overnight.
The mixture is warmed to room temperature and to it is added an aqueous solution of oxalic acid to destroy the excess DCC. The mixture is diluted with ethyl ether and 1V() ~) I /(I(IUU9 ~ ~ (~ I'CI~/ l!S90/03(72 -28_ filtered. The solid is washed with ethylacetate and the filtrate separated. 'fI-re organic layer is washed with to percent sodium hydroxide and then with water twice and brine once. The organic solution is next dried over magnesium sulfate and filtered. The solvent is removed to give a yellowish vi sCOUS oil which was clrromatographed on dry column silica gel using ethyl acetate/Irexane (1:2) as the solvent to give a yellowish viscous oil (890 mg).
This oil was solidified in petroleum ether to give a white solid, mp 77.5-79°C: IR (KBr) 1690, 1000, 7580 cm~~; ~Ii PIMR (CDC13) 1.2-1.6 (t, 3Ii, CHI3) , 2.82-3.28 (q, 2Ii, SCFiZ) , 3.37, 3.58, 4.49 and 4.69 (q, 2Ii, Cliz) , 4.99 (s, lFi, CHO) , 7.02-7.45 (m, 8H, aromatic) .
Anal. Calcd. for C»Ii~603S: C, 67.98; II, 5.37 Found : C, 67 . 8 ; 1i, 5 . 5 EXAM~'LE 12A
12H-Uibenzojd glfl 3ldioxocin-6-thivcarboxamide A stirred solution of 12II-dibenzo(d,g)[1,3) dioxocin-6-carboxamido (3.88 grams, 0.0152 mol) and Lawesson's reagent (3.69 grams, 0.00912 mol) in 40 ml of toluene is heated at rerlux. After 2.5 hours, the reaction is cooled to room temperature and concentrated under reduced pressure to afford a dark gummy residue.
Flash chromatography of this material (elution with CHZClz) affords 1.6 grams of product as a tan solid.
Recrystallization from hexanes results in 1.1 grams of product as an off white solid: mp. 165-169°C; IR (KBr) wo ~mooooo t~crius~~oio3~>7z 3380, 3140, 1615, 1440, 1220, 975 cm's; 'H NMR
(DMSO-db) 3.65 and 4.41 (2d, 2, 12a and 12b), 5.17 (s, 1, Fib) , 7.0-7.6 (m, 8, Ar-FI) .
Anal. Calcd. for C~5Ii~3NOZS: C, 66.4; ii, 4.8; N, 5.2 Found: C, 66.5; FI, 4.9; N, 5.1 ~;?CA1~~~ 13 12H-Dibenzofd,qlfl 3]d~ox_ocin~6-~ t i a To a stirred solution of 12F1-dibenzo[d,g] [1,3]
dioxocin-f-carboxamide (8.24 grams, 0.0323 mol) and pyridine (5.74 ml, 0.071 mol.) in 80 ml of 1,4-dioxane at 0°C, is added trifluoroacetic anhydride (5.0 ml, 0.0355 mol). After stirring for 5 minutes at 0'C, the reaction is warmed to room temperature and stirred for 3 hours.
'The volatiles are removed under reduced pressure, the residue taken up into ethyl acetate, washed with 1N NC1, fiz0, saturated aqueous NaIIC03, brine, dried over MgS04 and c~onceratrated to afford G.8 grams of a white solid.
Recrystallization from cyclohexane affords 5.46 grams (71 percent) of product as a wtrite solid; mp 127-130'C; IR
(KBr) 6.28, 6.71, 6.85, 7.44, 8.1, 8.45, 8.96, 13.1 cm'r;
~H NMR (60 MIiz, CDC13) 3.83 and 4.29 (2d, 2, CHZ) , 5.84 (s, 1, CFi) , 7.2-'7.0 (m, 8, Ar-FF) .
Anal. Calcd. for CrSFFrN02: C, 75.94; H, 4.07; N, 5.90 Found: C, 75.8; H, 4,0; N, 5.g 1V() 91/00(1(19 2 0 3 5 0 2 4 i~~ Iv ~59()/(»~,~2 ~X_J1M P LE 14 Sodium 12H-Dibenzo(_d ct1f1~7~c~icxocin-6-c~rboxvlate A solution of l2li-dibenzo[d,g][1,3)dioxocin-6-carboxylic acid (1.3 grams, 0.00507 mol.) and NaOIi (0.41 grams, 0.0101 mol) in 50 ml of metloanol is refluxed for 30 minutes. The reaction mixture is then concentrated under reduced pressure and the residue recrystallized from ethanol-water to afford 0.65 grams (45 percent) of product as a white solid: mp greater than 320°C; IR
(KBr) 3.0, 6.2, 7.0, 13.25, 8.35, 7Ø45, 13.3 cm-~; ~H NMR
(60 Mliz, Dz0) 3.3 and 4.4 (2d, 2~, Ctiz) , 4.8 (s, 1, CIi) , 6.8-7. 4 (M, 8, Ar-Fi) .
Anal. Calcd. for C~SII~~U4Na 1/2 It20: C, 62.7; H, 4.2 Found: C, 63.0; N, 3.9 ,~ X.AM E 15 Potassium 12H-Dibenzo_Ld,alI1.31~ioxocin-6-carboxylate A mixture of 12II-dibenzo[d,g)[1,3]dioxocin-6-carboxylic acid (5.0 g, 0.0195 mol) and potassium carbonate (1.95 g, 0.0195 mol) in 100 ml of water is stirred at room temperatture for 4 hours tlaen at 45 ° C for 2 hours . 'rhe reaction mixture is then cooled to room temperature, treated with charcoal and concentrated to afford a wet off-white solid. This material is recrystallized from ethanol to give 2.27 g (39.5 percent) of product as a white-gray solid: mp 275-290°C; IR (KBr) fV() 9!/00(1(19 I'Cf/LJS90/()3C72 ,r-- - 31. -2730-3600, 1610, 980, 760 cm-~; ~Ii NMR (CDC1~) 3.5 and 4.35 (2d, ?., CHZ) , 4.5 (s, 1, Iib) , G.8-7.5 (m, 8, Ar-I;) .
Anal. Calcd. for C~SIi»04K~1/2 II20: C, 59.4 ; H, 3.99 Found: C, 59.2; II, 4.5 ~XlIMPI.E 16 Diethanolamine Salt of 1211-Dibenzo[d,g)[1,3]dioxocin-6-carboxylic Acid To a stirred solution of 12H-dibenzo [ d, g] [ 1 , 3 ]
dioxocin-6-carboxylic acid (4.0 grams, 0.o15G mol) in 40 ml of tetrahydrofura» is added diethanolamine (1.64 grams, 0.0156 mol). after ?. hours at room temperature, the solids that formed are collected by filtration, washed with ether and dried to afford 5.04 grams (89 percent) of product as a white salad: mp 114-116'C; IR
(KBr) 3.0-4.0, 6.2.5, 6.'79, 7.05, 8.1, 10.35 cm-~; ~Ii NMR
(60 Mliz, DMSO-db) 3.05 (m, 4, (CIIzCIiZOIi)z) , 3.55 and 4.37 (2d, 2, CHZ) , 3.75 (m, 4, (CIIzCIIZOIi)Z) , 4.69 (s, l,Cli) , 6.4-7.5 (m, 12, Ar-Ii and 4 exchangeable) .
Anal. Calcd. for C~9IIz306: C, 63.15; Ii, 6.41; N, 3.88 Found: C, G3.2; ti, 6.4; N, 4.0 1fU cll/(IIIUOc) I'CI~/L1S90/03G71 ,._.. _ 3 2 ~?~~l.Pla~. 17 12H-L7ibenzo[d,g][1,3]dioxocin-G-carboxylic acid dimethyl amine salt 'to a solution of 1211-d.i.benzo[d,g][1,3]dioxocin -6-carboxylic acid (5 g, 19.5 mmol) in ethyl acetate/benzene is added excess liquid dimethylamine at 0 ° C under nitrogen. 'I'txe mixture i.s stirred overnight at room temperature under nitrogen. The resultant solid is filtered and dried to yield 5.5 g of white solid, mp 164-172°C: IR (KF3r) 1640 cm-~; ~H NMR (CUC13) 2.51 (s, 6H, NCI(3) , 3.47, 3.6, 4.25, and 4.4 (q, 21i, CHZ) , 4.55 (s, 111, CHCOZ) 6.8-7.5 (m, 81I, aromatic) .
Anal. Calcd, for C»1i~90,'N: C, 67.76; lI, 6.36; N, 4.65 Found: C, 67.7; II, 6.5; N, 5.0 EXAMPLE x8 4(2,2-Uimethyl-1,3-dioxolt~nyl)methyl 1211-dibenzo[d, g]
11.3] dioxocin-6-carbox_ylate 12H-Dibenzo[d,g][1,3]dioxocin-6-carbonyl chloride (10 g, 39 mmol) is dissolved in toluene and added to a solution of glycerolketal (5.6 ml, 45 mmol) and l0 ml of triethylamine i.n toluene at 0-10'C under argon. The mixture is heated at reflux for 5 hours, cooled to room temperature, poured into 150 ml of water and extracted with 4 x 1.50 ml of ethyl acetate. The organic solution is washed with 5 percent IIC1, 5 percent 1VU 91/00(10'l I'Cf/US9U/(?3(72 3 ~ ~ ~ 4 -33-NaOIi and then brine, dried with magnesium sulfate and filtered. The soJ.vent is removed and the residue chromatographed on dry column silica gel using ethyl ether/hexane (1:1) as the solvent to give a yellowish liquid which is crystallized in petroleum ether. The solid is filtered and washed with petroleum ether to give a white solid, mp 109-111°C: IR (KBr) 1780, 1581 cm-~, III NMR (CDC13) 1.4 and 1.47 (2S, 6Ii, CH3) , 3. 36, 3.58, 4.49 and 4 .7 (q, 2II, CIIZ) , 3.7-4.4 (m, 3Ii, C1I0 and CHzO) , 4.4-4. 6 (m, 2Fi, OCNZ) , 5.1 (s, 1H, OCIiO) , f . 95-7.45 (m, BII, aromatic) .
Anal. Calcd. for CZ~IIzZ06: C, 68.10; Ii, 5.99 Found: C, 68.3; Ii, 6.0 t4ethyl-6-Methyl-l2li-Dibenzo[d,g)(1,3)dioxocin-6-carboxvlate To a stirred solution of isopropyl cyclohexyl amrne (2.92 ml, 0.0178 mol) in 15 ml of dry tetrahydrofuran (THF) under. N2 at 0°C is added n-BuLi (11.84 ml of 1.5 M in hexane). After stirring 15 minutes at 0 ° C, the solution is cooled to -65 ° C and a solution of methyl l2li-dibenzo[d, g) (1,3)dioxocin-6-carboxylate (4.G g, 0.0148 mol) in 10 ml of TIiF is added dropwise over a period of 5 minutes. The solution is stirred at -65°C for an additional 10 minutes and then added via syringe over a period of 2 minutes to a solution of methyl iodide (1.84 ml, 0.0246 mol) in 25 ml of dry ~5'() ~) I /(IOflf)9 ~ I'CT/ US90/03Fr72 '"' -3d-dimethyl sulfoxide rat room temperature. After stirring for 30 minutes, the reaction mixture is diluted with 300 ml of Cli2Clz, washed with liz0, 1N FiCl and then brine, dried over MgS04 and concentrated. The residue obtained is purified by dry column chromatography (elution with 1:4 ethyl. acetate-hexanes) to afford 2 g of a yellow syrup. This material was subjected to IiFLC purification (Waters 500, 2 columns, 4 cycles, elution with 1:7 ethylacetate- hexanes) tU afford 1.1 g (2G percent) of lU product as a clear syrup: IR (neat) 5.65, 6.3, 6.7, 6.85, 7.25 cm~~; ~Ii NMR (60 Mliz, CDC13) 1.36 (s, 3, CII3) , 3.71 and 4.32 (2d, 2., CIIZ) 3.9 (s, 3, OCH3) , 6.95-7.4 (m, 8, Ar-II) .
Anal. Calcd. for Cr~II»04: C, 71.82; H, 5.67 Found: C, 71.8; H, 5.7 (cis and trans) Methyl-12-Methyl-l2li-Dibenzo[d,g)(1,3]
dioxocin-6-carbox~late A mixture of ?.,2'ethylidenebisphenol (10.0 grams, 0.0467 mol), d.ichl.oroacetic acid (3.85 ml, 0.0467 mol) and potassium carbonate (25.8 grams, 0.187 mol) in 200 ml of isopropyl alcohol is heated at reflux for 24 hours with vigorous stirring, after which an additional 3.85 ml of dichloroacetic acid is added and the mixture refluxed with stirring for 70 hours. The isopropyl alcohol is removed by distillation at atmospheric pressure and replaced gradually with IiZO. The reaction N'( ) 9 I /01111(19 2 0 3 5 0 2 4 i'~/us~o/o3«z mixture is cooled, acidified by addition of concentrated IiCl and extracted into chloroform. 'the chloroform extract is washed with brine, treated with charcoal, dried over MgS04 and concentrated to afford a quantitative yield of crude acid. This material is then converted to the methyl ester by refluxing in a methanol solution ( 100 ml ) in the presence of conc . IiZS04 ( 0 . 6 ml ) for 2 hours. The solution is cooled, 50 ml of CH2ClZ
is added and th e mixture neutralized by tire addition of solid NaZCO3. The inorganic salts are removed by filtration a nd the filtrate concentrated and taken up into CHZC12, washed with brine, dried over MgSO4 and concentrated to afford 11.5 grams of a dark semi-solid.

Dry column chromatography (elution with 1:4 EtOAc-hexane) lp yields 5.0 gr ams (38 percent) of product as a white solid consisting of a 1: 1 mixture of cis and traps isomers : mp 95-120'C; IR (thin film) 5.62, 6.7, 6.9, 8.2, 9.25, 10.05, 13.05 cm~~; rl-I NMR (60 Mliz, CUC13) 1.66 and 1.89 (2d, 2, CH3) , 3.88 and 3.95 (2s, 3, OCIi3) , 3.95 and 5.1 (2q, 2, CH) , 5.0 and 5.36 (2s, 1, CIi) , 7.0-7.5 (m, 8, Ar-H).

Anal. Calcd. for C»Hr604: C, 71.82; Ii, 5.67 Found: C, 71.6; Ii, 5.7 ethyl 12,12-Dimethyl-12~i-dibenzo[d,g][1,3]diaxocin-6-carboxvlate A mixture of ?.,2~-isopropylidene bisphenol (3.65 g, 0.01594 mol), potassium hydroxide (2.68 g of 85 W o 91 /nuoov I'Cf/US9t1/03G72 percent, 0.0478 mol) and dichloroacetic acid (1.31 ml, 0.01594 mol) in 65 ml of isopropyl alcohol is heated at reflex. After 20 hours at reflex, an additional 1.79 g of 85 percent KOH and 1..31 ml. of di.chloroacetic acid are added and the reaction mixture is heated at reflex for 2 days. The reaction mixture is then diluted with 200 ml of HzO, acidified by the addition of concentrated FiCl (10 ml) and extracted into ethyl acetate. The ethyl acetate solution is washed with brine, dried over MgSO4 l0 and concentrated. The residue is washed with petroleum ether to afford 3.7 g of crude product as a red-brown syrup. This material is then purified by an esterification-saponif.icati.on-esterification procedure (esterification agent mettaanol, llZSO4) . Ury column chromatography yield; 0.97 g of crude product, which is saponified (NaOH, Meoli-1120) , and purified by dry column chromatography to afford O.GO g of a white solid.
Esterification of this material (Et011, IIZS04) and purification by preparative thin layer chromatography (elution with 1:4 ethyl acetate-hexanes) yields 0.25 g of product as a clear syrup: IR (neat) 3.34, 5.65, 6.95, 8.2, 13.2 crn-~; rIi NMR (CDC13) 1.28 (t, 3, CIIzCH3) , 1.75 and 1.9 (2s, 6, (CIi3)ZC) , 4.24 (q, 2, CHZCH3) , (s, 1, CII) , 6.9-7. 6 (m, 8, Ar-Ii) ~ m/e 312.
Anal . Calcd. for C~911200,~: C, 73 . OG; Ii, 6, 45 Found: C, 72.4; Ii, 5.7 wo vtioouov ocriusvoio3o7z ~XI~MPLE ~ ~ 0 3 5 0 2 4 12H-Dibenzo[d,g)[1,3)dioxocin-12-hydroxy-6-carboxylic acid Lactone To a stirred sol.ut.ion of 12H-dibenzo [d, g] [ 1, 3 ) dioxocin-12-keto-6-carboxylic acid (10.U g, 0.0370 mol) and sodium hydroxide (1.63 g, 0.0407 mol) in 200 ml of 5:3 ethanol-water is added sodium borohydride (1.40 g, 0. 0370 mol ) and the reaction is heated to 55 ° C. After 16 hours at 55 ° C, the reaction is cooled to r oom temperature lU and poured cautiously onto 1 rlCl ( 500 ml ) , then extracted with ethyl acetate. Z'tne ethyl acetate solution is washed with brinE>., dried over MgS04 and concentrated to afford a quantitative yield of a mixture of alcohols and lactone. This mixture and p-toluenesulfonic acid (O.US g) in 250 ml of benzene is heated at reflux. After 2 hours, the reaction is cooled to room temperature, diluted with ethyl acetate and filtered to remove insoluble polymeric material. The filtrate is washed with saturated aqueous ldatrC03, then brine, dried over MgSO4 and concentrated to afford 6.1 g (64 percent) of a white solid (approximately 95 percent pure).
Analytically pure material is obtained by dry column chromatography (eluti.on with 1:2 EtOAc-hexanes) , followed by recrystallization from benzene-hexanes: mp 147-149°C;
IR (KF3r) 5.73, 6.74, 7.76, 8.41, 9.74, 13.36 cm't, tH NMR
(60 MriZ, CDC13) 5.97 (s, 7., CHC02-) , G.39 (s, 1, ArZCI_r-O) , 6.8-7.4 (m, 8, Ar-N) .
Anal. Calcd. for Ct5Hto0': C, 70.86; r1, 3.96 Found: C, 71.2; Ir, 4.0 1~'() ~)I/I111U119 I'('1'/USc)(1/1)3G72 E_X.III~FLE 23 Ethyl 1-Methyl l2ti-dibenzo[d,g]~1,3)aioxocin-6-carboxYlate A mixture of 6-methyl-2 , 2' -methylene bisphenol (3.1 g, 0.0145 mole), potassium hydroxide (2.87 g of 85 percent, 0.0434 mol) and dichloroacetic acid (1.2 ml, 0.0145 mol) in 55 ml of isopropyl alcohol is heated at reflux. After 22 hours at reflux, an additional 1.91 g of 85 percent KOH and 1.2 ml of dichloroacetic acid are added and the reaction mixture is refluxed for 4 hours.
'fhe reaction mixture is then cooled, diluted with 150 ml of Ii20, acidified by the addition of concentrated IiCl and extracted into ethyl acetate. The ethyl acetate solution is washed with brine, c:iried over MgS04 and concentrated to afford the crude acid as a gummy yellow-tan solid. A
solution of the cruc:te acid and concentrated IizS04 (0.2 ml) in 25 ml of ethanol is heated at reflux.
After 2 hours, the solution is cooled to room temperature , diluted w.i.th Cli?Cl.z ( 15 ml ) and neutral ized by tire addition of solid NazC03. The inorganics are removed by filtration and the filtrate is concentrated under reduced pressure. Ttae residue obtained i.s taken up into etluyl acetate, washed with IIzO, then brine, dried over MgS04 and concentrated to afford 3.9 g of an amber syrup. Dry column chromatography (elution with 1:4 ethyl acetate-hexanes) followed by recrystallization from ~1'() 91/tltltltly 1'C1~/US')0/03C7Z
-3g- ~ 0 3 5 0 2 4 cyclohexane yields 1. () g of product as a white solid:
mp 78-83'C; IR (KE3r) 1759, 1205, 1065, 98U c:m-~; ~I1 NMR
(CDC13) 1.41 (t, 3, CII?~3) , 2.52 (s, 3, CIi3) , 3.69 and 4.45 (2d, 2, (AR)2-CIi?) , 4.4 (q, ?_, CIizCIl3) , 5.05 (s, 1, CIi), 6.85-7.5 (m, 7, Ar-Ii); mass spectrum, m/e (M+) 298.
~~I1MPLE 24 Methyl 2-Methyl-12H-dibenzo[d,gJ[1,3)dioxocin-6-carbox_y_late into a 3-neck round bottom fl<zsk fitted with a mechanical stirrer and a condenser, is placed 4-methyl bis (1-hydroxy-2-phenyl)-methane (10.2 g, 48 mmol) and potassium carbonate (26.33 g, 19U mmol.) in 200 ml of isopropanol. Dichloroacetic acid (3.93 ml, 48 mmol) is then added and the mixture is heated at reflex for 1 day.
More dichloroacetic acid (3.93 ml, 48 mmol) is added and reflex is resumed for 3 more days. 400 ml of water is then added arod the mixture is acidified with hydrochloric acid. After stirring tire mixture for 2 hours at room temperature and extracting with 200 ml of ethyl acetate twice, the combined organic layer is next washed with 200 ml of 1M HCl and 150 ml of brine, dried with magnesium sulfate and filtered. The solvent is removed, yielding about 17 g of brown oil. This oil is used directly for esterification. It is dissolved in 150 ml of methanol and 0.3 ml of concentrated sulfuric acid is added. The mixture is heated to reflex for 2 hours and then cooled to room temperature. Sodium carbonate is added and the mixture is stirred for ~ luour. Following filtration of ..., ~","wm I'C'I~/US90/U3G72 20~5Q24 -4"
the mixture, the solvent is removed and the crude solids dissolved in methylene ctvloride, washed with 100 ml of 5 percent sodium hydroxide slid 150 ml of brine, dried with MgSO~ and filtered. 'floe solvent is then removed to yield about 7 g of brown solid, which is chromatographed on dry column silica gel using ethyl ether/hexane as the solvent to give about 5.5 g of wtoite solid. This solid was re-crystallized in ethyl ettrer/hexane to give 4.51 g of white solid. mp lUG-1U8.5'C. IR (KBr): 1761, 1748 cm~~. ~H NMR (CDC13) : 2.27 (s, iii, CH3) , 3.3, 3.5, 4.46 and 4 . 67 (q, 2H, CFI) , 3.92 (s, 3H, OCIi3) , 5.02 (s, lli, CfiO) , 6. 85-7 . 5 (m, 7II aromatic H) .
Anal. Calcd. fox C~THi~6iiG: C, 71.82, H, 5.67 Found: C, 71.5; Ii, 5.7 ~XI~M~LE 2~
3-Methyl-12-H-dibenzofd alf1~.31dioxocin-6-carboxylic acid To a suspension of sodium hydride (5.7 g of a 50 percent dispersion in oil, washed with petroleum ether; 0.1193 mol) and 18-crown-6 (0.45 g) in 65 ml of 1,4-dioxane is added slowly, dropwise, a solution of dichloroacetic acid (4.0 ml, 0.049 mol) in 65 ml of 1,4-dioxane over a period of 15 minutes, followed by the dropwise addition of 5-methyl-2,2'methylenebisphenol (6.36 g, 0.0297 mol) in 85 ml of 1,4-dioxane over a 2 5 period of 4 5 minutes . The reaction mix is them heated at about 90°C for 18 hours and then at reflux for 4 hours.
Next, it is cooled to room temperature, poured onto ~V() 91/()0(109 I'C.'f/llS9()/(?3672 600 ml of H2o, acidified by the addition of concentrated HC1 and extracted with ethyl acetate (2 x 500 ml). The ethyl acetate extract, is washed with brine, dried over MgS04 and concentrated to afford 9.9 g of crude product as a semi-solid. Purification via extraction with cyclohexane in a Soxhlet apparatus yields 5.0 g (62.3 percent) of product as a white solid: mp 149-152'C; IR
(Ki3r) 1730, 1245, 122.0, 1015 cm~r; riI NMR (DMSO-d6) 2.2 (s, 3, CFi3) , 3.54 and 4.3 (2d, 2, htZa -+- Iir2b) , 5.01 (s, 1, 116) , 6.8-7.5 (m, 7, Ar-Ii) .
anal. Calcd. for C~611~404; C, 70.7; Ii, 5.3 Found: C, 71.1; Ii, 5.22 ~X PLE 26 Methyl 4-methyl-12H-dibenzo[d,g)[1,3)dioxocin-6-carboxvlate n mixture of crude 6-methyl 2,2'-methylene bisptrenol (7.0 g, 0.0327 mol), potassium hydroxide (5.5 g, 0.098 mol) and dichloroacetic acid (2.7 ml, 0.037_7 mol) in 130 ml of-. isopropyl alcohol is heated at reflux for 23 hours, following which an additional 5.5 g of potassium hydroxide (0.098 mal) and tt-ren 2.7 ml of dichloroacetic ac.i.d (0.0327 mol) are added and the reaction mixture is again heated at reflux for an additional 3 hours. 'fhe mixture is then cooled to room temperature, diluted with 4U0 ml of water, acidified by the addition of concentrated IIC1 (15 ml), extracted with ethyl acetate (200 ml) and tine resultant organic solution 1V() 91/00009 I'('1'/US90/03~~72 "'° -42-is washed with brine, dried over MgS04 and concentrated.
The residue is then co-evaporated with toluene to afford g of crude acid as a tan solid. A solution of the crude acid and concentrated IIzS04 (0.6 ml) in 100 ml of 5 methanol is heated at reflux for 2 hours, after which the reaction mixture is cooled to room temperature, diluted with 25 ml of CFi2C1 and neutralized by the addition of solid NaZCO3. The inorganic salts are removed by filtration and the filtrate concentrated under reduced 10 pressure. The residue is taken up into a mixture of EtOAc-ether, washed wittn water, 5 percent aqueous NaOIi, then brine, dried over. MgSO4 and concentrated to afford 7.0 g of a yellow syrup. Ury column chromatography (elution with 1:4 EtOAc-toexanes) afforded 4.1 g (44 percent) of product as a white solid; greater than 95 percent purity. Recrystallization from cycloh exane afforded 2.1 g (23 percent) of pure product: mp 107-109?; IR (KBr) 5.74, f.97, f3.3, 9.5, 10.2, 13.5 cm's;
rIi NMR (90 MHz, CDC13) , 2.23 (s, 3, CIi3) , 3.41 (d, 1, Ii-CH) , 3.95 (s, 3, OCII3) , 4.62 (d, 1, fi C-Ii) , 5.04 (s, 1, OCH_O), 6.9-7.4 (m, 7, Ar-Ii).
Anal. Calcd. for C»II~604: C, 71.(32; II, 5.67 Found: C, 71. Q; Ii, 5.6 ~CI1M_pLE 27 2-Methoxyethyl l2li-Dibenzo[d,gJ[1,3)dioxocin-6-carboxylate l2li-Dibenzo[d,gJ(l,3Jdioxocin-6-carbonyl chloride (5.33 g, 19.5 mmol) is dissolved in toluene and wo m/uoo°v I>CI~/usv0/(13~~72 added to a solution of 2-methoxyethanol (2.2 ml, 27.6 mmol) and 7 ml of triethylamine in toluene at 0 ° -10 ° C under argon. The mixture is heated at reflux for 3 hours, cooled to roam temperature, poured into 150 ml of water and extracted witty 4 x 100 ml of ethyl acetate.
The resultant organic solution is washed with 5 percent hydrochloric acid, 5 percent sodium hydroxide and brine, dried with magnesium sulfate and filtered. The solvent is removed to give a brownish solid which is chromatographed on dry column silica gel, using ethyl ether/hexane (1:1) as the solvent, to give a yellowish oil. This oil is solidified, th a solid is filtered and washed with ethyl ether/hexaroe to yield a white solid:
mp 74-76°C: IR (KBr) 1779, 1581 cm~~; ~Ii NMR
(CDC13) 3.42 (s, 31i, CF13) , 3.3-4. 0 (m, 3H, CIi and OCIiz) , 4.35-4.8 (m, 3Ii, CIi and OCIi2) , 5. 1 (s, 1H, OCHO) , 6.9-7.45 (m, 8H, aromatic).
Anal. Calcd. for C~olIy805: C, 68.78; 11, 5.7'7 Found: C, 69.1; Fi, 5.9 2-Ethylhexy112H-Dibetyzo I d , c~ ~ ~ ~. , 3 ] dioxocin-6-carboxylate To a stirred solution of 12H-dibenzo[d, g]
dioxocin-6-carbonyl chloride (4 g, 0.015 mol) in 45 ml of toluene is added a solution of 2-ethylhexanol (2.28 g, 2.5 0 . 017 mol ) and 4 ml of trietlrylamine in toluene at 0' C
under argon. The mixture is heated at reflux for 2 hours, cooled, washed with 5 percent Na0lI and then brine, dried with magnesium sulfate and filtered. The solvent ~1'() 91/(1011(19 I'('I~/US9(1/03G72 is removed to give a brown liquid which is chromatographed on dry column silica gel using ethyl ether/hexane as the solvent to yield a yellowish oil (4.5 g) : IH (neat) 1770, 1500 cm's. ~Ii NMR (CDC13) 0.5-2.0 (m, 15H, CtIZ and Cli3) , 3.33, 3.53, 4.48, and 4.68 (q, 2H, CHZ) , 4.15-4. 35 (d, 211, OCFIz) , 5.2 (s, 1H, CH) , 6.9-7.4 (m, 8H, aromatic).
Anal . Calcd. for CZ3112$O4: C, 74 . 97; F1, 7 , 66 Found: C, 75.1, ti, 7.9 Ethyl 3-t-~3uty1-l2Hi-dibenzo [d, g] [ 1, 3 ]dioxocin-6-carboxylate A mixture of 4-t-butyl-2, 2' -mettrylene bisphenol (3.67 g, 0.0143 mol), potassium hydroxide (2.84 g of 85 percent, 0.0429 mol.) acrd di.chloroacetic acid (1.18 ml, 0.0143 mol) in 55 ml of isopropyl alcohol is heated at reflux. After 17 hours at reflux, an additional 1.90 g of 85 percent KOIi and 1.18 ml of dichloroacet.ic acid is added and reflux is continued for 4 hours. Thereafter, the reaction mixture is cooled to room temperature, diluted with 150 ml of 1120, acidified by tire addition of concentrated HiCl and extracted into ethyl acetate. The ethyl acetate solution i.s washed with brine, dried over MgS04 and concentrated to afford crude acid as a yellow-brown syrup. A solution of the crude acid and p-toluene sulfonic acid (U.07 g) in 25 ml of 10:1 C1iC13-ethanol is heated at reflux for 1.5 hours with azetropic removal of water. TOe solution is then cooled 1fU ') I /t10t1(Iy fCI-/US9U/03672 to room temperature, diluted with 50 ml of CIiCl3, washed with HZO, 5 percent aqueous NaOIi a:ad then brine, dried over MgS04, and concentrated to afford 3.93 g of a yellow-brown syrup. Dry column chromatography (elution with 1:4 EtOAc-hexanes) yields 2.4 g (49 percent) of product as a cloudy syrup: IR (neat) 2975, 1770, 1755, 1485, 1410, 1260, 76 em-~ f ~I1 NMR (CDC13) 1.24 (s, 9, C(CIi3)3) , 1.43 (t, 3, CIIZC~3) , 3.43 and 4.51 ( 2d, 2 11RZCIiz) , 4 . 39 (q, 2, CIIZCIi3) , 5. 05 (s, 7.0-7.4 (m, 1 CIi) , 7, Ar-II) ; mass spectrum, m/e (M-H) 340, (M+ - CH3) 323, (M+ - CH3CIIzOH) 294, (M+ - C4119) 283, (M+ - COZEt) 267.

~XhMPLE 30 Ethyl3-Trifluorometlryl-l2tl-dibenzo [d, g ] [ 1., 3 ] dioxocin-6-carboxylate To a suspension of sodium hydride (2.55 g of a 50 percent dispersion in oil, washed with petroleum ether., 0.0531 mol) amd 18-crown-6 (0.?. g) in 30 ml of 1,4-dioxane is slowly added dropwise, a solution of dichloroacetic acid (1.81 ML, 0.0219 mol) in 30 ml of 1,4-dioxane over a period of 15 minutes, followed by the dropwise addition of 5-trifluoromethyl-2,2~-methylene bisphenol (3.56 g, 0.0133 mol) in 40 ml of. 1,4-dioxane over a period of 45 minutes. The reaction is then heated at reflux for 20 I-yours, cooled to room temperature, poured into 300 ml of HzO, acidified by the addition of concentrated IiCl, amd extracted with ethyl acetate (2 x 200 ml). The ethyl acetate extract is washed with brine, dried over MgS04 alld concentrated to afford an wc) viiooao~~ t~c'riusooio3o~z oily residue which i ~ .further washed with petroleum ether to give 4.6 g of an orange-yellow semi-solid. A solution of this material and p-toluene sulfonic acid (0.07 g) in 30 ml of 10:1 CHC13-ethanol is heated at reflux for 1 hour with azetropic removal of water. The solution is then cooled to room temperature, diluted with 50 ml of CHC13, washed with Ii2U, 5 percent aqueous Na0li, and then brine, dried over MgS04, and concentrated to afford 3.75 g of a dark residue. Flash chromatography of this material (elution with 1:6 ethyl acetate-hexanes) affords 1.91 g (41 percent) of product as a white solid:
mp 78-81°C; IR (KBr) 1765, 1325, 1115, 990 cm's; ~Fi NMR
(C()C13) 1.41 (t, 3, CHzCII3) , 3.52 and 4.51 (2 d, 2, H~Za, Ii~Zb) , 4.41 (q, 2, CEi2C113) , 5.09 (s, 1, H6) , 7.0-7.5 (m, 7, Ar-fi) .
Anal. Calcd. for C~etl~SF304: C, 61.37; H, 4.29 Found: C, 61.41 H, 4.2 ~XA LE 31 Methyl 4,8-Dimethyl 17.H-dibenzo[d,g][1,3]dioxocin-6-2o carboxylate _ A mixture of 2,2'-methylene bis-6-methyl phenol (4.0 g, 0.0175 mol), dichloroacetic acid (1.45 ml, 0.0175 mol) and potassium carbonate (9.7 g, 0.070 mol) in 100 ml of isopropyl alcohol is heated at reflux for 24 hours with vigorous stirring after which an additional 1.45 ml of dichloroacetic acid is added and the mixture refluxed with stirring for 70 trours. The isopropyl alcohol is removed by distillation at atmospheric 1VU ~) i /(lU(l0y I'Cl'/ US90/03G72 pressure and replaced gradually with IizO. The mixture is cooled to 0°C and the solids collected by filtration.
Water (75 m) is added to ttoe solids and the mixture made strongly acidic with concentrated IiCl. The mixture is extracted into CIizClz, washed with brine, dried over MgS04 and concentrated to afford 3.0 g (73 percent) of the carboxylic acid. Esterification (methanol, FiZSO4, reflux) followed by dry column chromatography (elution with 1:4 ethyl acetate- hexanes), affords 1.9 g (50 percent) of product as a white solid: mp 134-135°C; IR
(KBr) 5.65, 6.72, a.2, 13.1 cm~~; ~Ii NMR (60 Mliz, CDC13) 2.21 (s, 6, 7 CH3) , 3.3F3 and 4. G2 (2d, 2, CHZ) , 4.0 (s, 3, CH3) , 4.99 (s, 1, CIi) , 6.9-7.3 (m, 6, Ar-H) .
Anal. Calcd. for Creiirn04.1/4 Ii20: C, 71.4; H, G.16 Found: C, 71.2; II, 6.1 XII~P~E 3 2 Methyl 4,a-Dichloro l2Fi-dj_benzo[d,g][1,3]dioxocin-6-carboxYlate A mixture of 2 , 2' -rnethylene bis-6-chlorophenol 7.0 (10.0 g, 0.0372 mol), diclrloroacetic acid (3.07 ml, 0.0372 mol) and potassium carbonate (20.6 g, 0.149 mol) in 150 ml of isopropyl alcohol is heated at reflux for 24 hours with vigorous stirring after which an additional 3.07 ml of dichloroacetic acid is added and the mixture refluxed with stirring for 67 hours. The isopropyl alcohol is removed by distillation at atmospheric pressure and replaced with water, gradually. The reaction mixture is cooled, acidified by addition of ~V() 91/UOIIU9 I'CT/US90/03G72 2p35p24 -4Ei-concentrated HC1 and extracted with CIiCl3. The chloroform extract is washed with brine, treated with charcoal, dried over MgS04 and concentrated to afford 12.39 of crude carboxylic acid. Esterification (methanol, IizS04, reflux) followed by dry column chromatography (elution with 1:4 ethyl acetate-hexanes) affords 5.29 g of product as a white solid:
mp 114-116°C; IR (KBr) 5.65, 6.95, 8.29, 9.47, 10.3 cm's:
~H NMR (60 MHz, CDC13) 3.4? and 4.67 (2d, 2, Cliz) , 3.99 (s, 3, CH3), 5.04 (s, 1, CII), 6.9-7.3 (8, m, Ar-H).
Anal. Calcd. for C~6II~zClz04: C, 56.66; Ii, 3.57 Found: C, 56.7; II, 3.5 3,9-Dimethyl-12H-dibertzo[d,g][1,3]dioxocin-G-carboxylic acid A mixture of 2 , 2' -methylenebis ( 5-methylphenol ) (8.3 g, 0.0364 mol), dichloroacetic acid (3.0 ml, 0.0364 mol) and potassium carbonate (20.1 g, 0.145 mol) in 220 ml of isopropyl alcohol is heated at reflux for 24 hours with vigorous stirring after which an additional 3.0 ml (0.0364 mol) of dichloroacetic acid is added and the mixture is refluxed for an additional 72 hours. The isopropyl alcohol is distilled off and replaced with water. The reaction mixture is then cooled to room temperature and aci_di.fi.ed by the addition of concentrated HC1 (35 ml). The solids that form are collected by filtration, taken up into ethyl acetate and the ethyl acetate solution is washed with 1N IIC1, then brine, dried v~o mnnonv ncrius~uio:~c,~2 over MgS04 and concentrated to afford a quantitative yield of crude product as n tan solid. Extraction of the crude product with hot cyclohexane in a Soxhlet extraction apparatus results in 4.55 g (44 percent) of product as a white solid from the cooled cyclohexane solution. Recrystallization from benzene-hexanes yields an analytically pure material: mp 172-174'C; IR (KBr) 3.4, 5.8, 8.0, 8.9 cm's; III tJMR (60 MHz, DMSO-db) 2.21 (s, 6, 2 CH3) , 3.52 (d, 1, II-C-Ii) 4.23 (d, 1, H-C-H) , 6.8-7.4 (6, m, Ar-H).
Anal. Calcd. for C»I-I~oo4: C, 71.82; Ii, 5.67 Fot.rnd: C, 72.1; ~H, 5.7 ~XN~ E 3 4 Methyl 3,9-Dimethoxy-J.2II-dibenzo[d,g][1,3]dioxocin-6-carboxylate 'to a solution of_- potassium hydroxide (1.29 g, 23 mmol) in 100 ml of isopropanol is added 1, 1'-methylene bis(4-methoxy-2-phenol) (1.8 g, 6.9 mmol) and then, O. G ml of dichloroacet.i.c acid (7.2 mmol) . The mixture is heated at reflux overnight. The mixture is then cooled to room temperature and potassium hydroxide (1.29 g, 23 mmol) and dichloroacetic acid (0.6 ml, 7.2 mmol) are added. The mixture is again refluxed overnight. The solvent is removed on n rotavap and water is added. The mixture is then acidified with concentrated hydrochloric acid and extracted with ethyl acetate three times. The organic layer is washed with brine, dried with magnesium 1V() 91 /UQOiI'l I'CfI tJS90/03C72 -5°- 2035024 sulfate and filtered. The solvent is removed, leaving a yellow oil. This oil is dissolved in 30 ml of methanol and 1 ml of boron trifltroride etherate is added. The mixture is next stirred at room temperature for 4 hours, poured into saturated aqueous sodium chloride ( 50 ml ) and extracted with ethyl acetate three times. The resulting organic solution is washed with 5 percent sodium hydroxide (50 ml) and brine, dried with magnesium sulfate and filtered. The solvent is removed to leave a yellow l0 oil which is chromatographed on a dry column silica gel using ethyl acetate/hexane (2:1) as the solvent to give a white solid (1.16 g), mp 102-106'C: IR (YI3r) 1750, 1620, 1505 cm -~. ~Hi NMR (CDC13) 3.25, 3.4, 4.31 and 4.45 (q, 2Ii, Cliz) , 367 (s, GII, OCIi3) , 3.9?. (s, 3Ii, OCIi3) , 5.06 (s, 2Ii, OCH) , 6. 5-7.25 (m, 6Ii, aromatic) .
Anal. Calcd. for C~8H~e06: C, 65.45; Ii, 5.49 Found: C, 65.2; Ii, 5.5 Methyl 4-t-Butyl-1211-dibenzo[d,g][1,3)dioxocin-6-carboxylate To a suspension of sodium hydride (1.65 g of a 50 percent dispersion in oil, washed with petroleum ether, 0.0343 mol) and 18-crown-6 (0.13 g) in 16 ml of 1,4-dioxane is added slowly, dr~pwise, a solution of dichloroacetic acid (1.17 ml, 0.0142 mol) in 18 ml of 1,4-dioxane over a period of 15 minutes followed by the dropwise addition of 6-t-butyl-2,2'-methylene bisphenol 1V(> 91/11(1009 i'CI~/LJS90/03C,72 °°' - 51-(2.2g, 0. 00858 mol) in 21 ml of 1, 4-dioxane over a period of 25 minutes. The reaction mixture is then heated at reflux. lifter 24 hours at reflux, the reaction mixture is cooled to room temperature, poured into 150 ml of lizo, acidified by the addition of concentrated HCl (10 ml) and extracted with ethyl acetate (2 x 100 ml). The extract is washed with brine, dried over MgS04 and concentrated to afford crude carboxylic acid as a yellow-brown syrupy residue. This material is taken up into ether (15 ml) and treated with excess ethereal diazomethane (about 0.6 g in 30 ml of ether). After standing overnight at room temperature, the reaction mixture i.s evaporated and the residue purified by dry column chromatography (elution with 1:4 EtOAC-hexanes) to afford 0.66 g of slightly impure product. Preparative TLC (elution with 1:10 ether: petroleum ether) yields 0.44 g (16 percent) of pure product as an off white solid: mp 113-117°C; IR
(KBr) 2950, 1760, 1205, 970 cm-~; ~1i NMR (CUC13) 1.3 (s, 9, (CIi3)3C) , 3.42 and 4.6 (2d, 2, C1IZ) , 3.94 (s, 3, COOCII3), 5.05 (s, 1, CH), 6.97-7.4 (m, 7, Ar-H).
Anal. Calcd. for CZOiizz04: C, 73.6; Ii, 6.79 Found: C, 73.5; N, 7.0 ~l~MPLE 3 6 4-Methyl-1211-dibenzo[d,g][1,3]dioxocin-6-carboxylic acid, diethanolamine salt A solution of 4-methyl-12H-dibenzo[d, g)[1,3]
dioxocin-6-carboxylic acid (0.64 g, 0.00237 mol) and ~VU 91/00009 I'Cf/US90/03f72 w...
2 0 ~ 5 0 2 4 -52-diethanolamine (0.25 g, 0.00237 mol) in 6.4 ml of TFiF is stirred at room temperature. After 18 hours, the clear solution is concentrated under reduced pressure and the residue stirred for 1 hour with 15 ml of ether. The ether is then decanted away, leaving a clear syrup which is dried under vacuum to a.ffard 0.88 g (99 percent) of a white hygroscopic cryst~alli.ne foam: IR (thirn film) 3.0, 6.15, 8.12, 10.32; ~Ii NMR (CDC13) 2.2.1 (s, 3, CH3) , :F . 1-3 . 5 (m, 5, 2 CIiZ and (Ar. ) z-C-~I) , 3 . 8-4 . 2 (m, 4 , 2 lU CIIZ) , 4.45 (d, 1, (Ar)z-C-~) , 4.8 (s, 1, CII) , 6.8-7.4 (m, 7, Ar-Ii) .

N-Phen_Yl= l2Fi-dibenzofd,a1 f 1~ 3ldivxocin-6-carboxamide To a stirred solution of crude 12H-dibenzo[d,g][1,3]dioxocin-6-carboxylicacid chloride(4.3 g, 0.016 mol) and triethylamine (3.3 ml, 0.24 mol) in 40 ml of toluene was added dropwise a solution of aniline (1.6 ml, 0.017 mol) in 10 ml of toluene over a period of 5 minutes. After being stirred 4.5 h at RT, the reaction was filtered to remove the insolubles that formed. the filtrate was concentrated under reduced pressure. The residue obtained was purified by dry column chromatogr,phy (elution with 1:2 ethyl acetat-hexanes) to afford 3.2 g of product. Recrystallization from ethyl acetate-hexanes gave 1.8 g (35%) of product as a white solid: mp 164-165:0; IR (ICI3r) 6.0, 6.79, 6.97, 8.28, 10.35, 13.27m; ~H NMR (60 MIIz, CUC13) 3.45 and 4.55 (2d, 2, CHz) , 5. 07 (s, l, CII) , 7.0-8. B (m, 8, Ar-Ii) , 8.6 (b, l, NII) .

1f() 91/(111()09 I'CT/US9(1/03C72 _53_ Anal. Calcd. for CZ~II»03N: C, 76.1; Ii, 5.2: N, 4.2.
C, 76.0; It, 5.3; N, 4.3 1-Aza-12H-Dibenzo[d.ct]j113]dioxocin-G-carboxylic acid To a suspension of sodium hydride (4.93 g of a 50% dispersion in oil which was washed with petroleum ether, 0.1 mol) and 18-crown-6 (0.39 g) in 55 ml of 1,4-dioxane was added dropwise a solution of dichloroacetic acid (3.5 ml, 0.04 mol) in 55 ml of 1,4-dioxane of a period of 15 min. followed by the dropwise addition of 3-hydrosy-2-(2'-hydroxybenzyl)pyridine (5.17 g, 0.026 mol) in 75 ml of 1,4-di.oxane of a period of 40 minutes. The reaction was then heated at reflux. After 24 h at reflux the reaction was cooled to room temperature, poured onto 500 ml of IizO, cautiously neutralized by the addition of 1H IiCl and extracted wi.tii ethyl acetate ( 3 x 500 ml ) .
The ehtyl acetate extract was washed with brine, dried over MqSO~ and concentrated to afford the crude carboxylic acid as a yellow-brown solid.
Recrystallization from methanol gave 1.5 g (23~) of pure product as an off white solid; mp 224-227:C (d) ; IR (KF3r) 1748, 1440, 1225, 9'75 cm-~; IIi NMR (DMSO-d6) D=d3.8 and 4. 55 (2d, 2, Ii~zA arid 11f2~) , 5.2 (s, 1, 116) , 7.0-7.5 (m, 6, Ii3, I(4, Iie, H9, Ii~o, II~~) , 8.2 (m, 1, Hi2) .
Anal. Calcd. for C~~II»N04. s IiZO: C, 63.15, Ii, 4.5; H, 5.3 C, 63.0; I-i, 4.2; H, 5.0 wo ~~ i iuuuuy t~criusyoio~~~7z '~ -54-~li~.~ES 39 THROUGH 97 Additional examples of compounds that fall within the scope of the present invention are described in Table A. These were prepared by procedures analogous to those given in the preceding examples.

1V() 91/01)009 5 5 I'CI'/US90/03G72 vmn vw vl n n n n n n n n n n w :
m n W N O ~ poV P ~ t' w N O ~O

A
~ ~ ~

n n n n n [~n n n n n ~~n n n i 2 A 3 5 0 2 4 8 8 ~ z ~ ~ ~ ~ ~ n n n n n x n n x n x x x x 7 x n x x x x x x x x z n n i a:~

n ,~ ~ x x x ,~z z n ~ x xrv x o =

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1V() 91 /(1110()9 !'f-'1'/L ~~'W~tt3G72 Pre and Post Emergent iie~bic~.dal Activity The herbicide screening test is designed to identify compounds that exhib3.t pre-emergence (Pre) and/or post-emergence (Post) herbicidal activity.
Plantings of the indicated test species are seeded in separate fiber pans (E3" X 10" X 3" deep) containing pasteurized soil. Tfae POSt pans are seeded two weeks prior to treatment. 'fhe I're pans are seeded one day prior to application of the test compounds. One Pre and one Post pan is employed for each compound, unless otherwise indicated. Prior to application of the test formulation, the Pre pans are mist watered to stabilize the soil surface. The standard laboratory formulation at the 8 kg/ha treatment rate is prepared by weighing 73.6 mg of the test compound into a 125 ml flask to which is then added 40 ml of acetone followed by 4U ml of 0.1%
Ortho X-77 surfactant. If the test compound appears insoluble in the formulation, it is treated for 1-2 minutes with an ultrasonic probe. If still insoluble, the particle size is reduced by grinding to a size sufficient to allow it to pass through the spray nozzle.
Following preparation of the test formulations, each is then sprayed equally and completely on the Pre and Post pans employing a handheld spray gun with an air atomizing nozzle. Acetone is employed to rinse the spray gun between application of each formulation. Tine treated pans are then moved to a growth room, or greenhouse, where they are maintained and appropriately watered for 13 days following treatment. At this time, the pans are ivo ~munocw rc-rw~s~oio~f,~z 2 Q 3 5 0 Z ~"59-then evaluated to determine the percent kill/inhibition/
suppression relative to an untreated control. The rating numbers range from 0, indicating no injury, to 100, indicating complete kill or control. Compounds that show 80~ control Post and 50~ control Pre against any 3 species are considered for further testing. Results are shown in the following Table.

1'~'() J I /001109 I'Ct'/US90/03G71 -GO-o ~

l11 O O O O O O O O O O O O O O
O O O O O

H ~ N r'1 ~ r-1 tIW D 1n N ~O N C1 N ~O
N N N

~0~5024 In o 0 0 0 0 0 o a o 0 0 0 0 0 0 ("1 N h N U'1 ri N rl r-i Pa Ir1 V7 O O O 1f1 O O O O O O O O O O O
O O O O O

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r-1 e--I fV

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(n ~ V71 O O O u1 O O O O O O O O O O O
O O O O O

Cx ~O CO M N N N u1 tV N tp f-1 rW-1 M
~O r1 '-1 '-1 H ~-1 cI1 U

x f-~~ ~n o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 N N t"1 f1 -1 1D h ~O lf1 1p t'1 l0 N l11 lf) f'1 N

'~ C~ O O O O O O O O O O O O O O O O
F-I) O O O O

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T'he followi.rag examples and tables illustrate some of the plant growth regulation activities of the glyoxylate compositions of the present invention.

Effect on 'Turf Growth The acid form of the glyoxylate prepared in Example 1 was evaluated as a turf growth retardant on four grass species at varying rates as indicated in Table 2.
l0 Turf species were planted in 8 by a cm fiber pots using steam pasteurized soil, and allowed to grow until well established, i.e., roots extended to the bottom of the fiber pot. The turf was clipped periodically to keep the thatch at a manageable level and fertilizer was applied on a regular basis. Prior to application of the compound to the turf, the grass was cut to vne cm. The compound was formulated in 15 X 125 mm disposable test tubes and f~liar applications were made in a hood using a UeVilbliss Model EGA-502 hand held sprayer.
height measurements were taken two weeks after application of the compound, with the results set forth in Table 2.
..

W() 91/OU009 I'C1'/US90/03G72 ,.~.. _ 7 0 _ TAFiLE 2 IIEIQHT* ( cm) RATE
kg/ha FEBTUCA POA FEBTUCA LOLIUM
ARUNDINACEA PRATENf3I8 RUBRA PERENE

0.1 5 5.5 4 4 0.5 3 3.5 3 2.5 1.0 2.5 3.5 3 2.5 2.0 2 1.5 3 2 4.0 1 1 2 1.5 Check 6 7 4 4.5 * Average of two replications Despite some phytotoxicity~observed with this method of application, good retardant effect, especially on Kentucky Bluegrass, was demonstrated.
E~ChMPLE 100 Effect of Application Method vn Turf Retardancy Using the turf species set forth and grown as in Example 99, the effect of the method of application of the compounds of Examples 1G and 2 is evaluated, with results set forth in 'fable 3. Weight measurements are taken by cutting eac:li turf pot, after two weeks, to a uniform height, combining the clippings from all species and oven drying prior to weighing.

1fU 91 /()11()09 ,,- _ 71 _ I'CT/ US90/03G72 RATE LRY WEIGHT* g/ha) CoMP (k OUZID kg/ha FOLIAR BAIL GRANULAR
DRENCH

Example 16 0.25 1.78 2.26 1.58 0.50 1.11 2.25 1.08 1.0 0.75 1.06 1.10 2.0 0.55 0.65 0.52 Av. 1.05 1.55 1.07 Example 2 0.25 1.10 1.51 2.44 0.50 1.45 U.83 2.48 1.0 1.12 0.72 2.10 2.0 1,2p 0.32 2.03 Av. 1.21 0.84 2.26 Check -- 2.49 2.49 2.49 * Average of two repl~.cations Granular application is found to result in the lowest degree of phytotoxicity to the grass species.
l0 EXAMPLE 101 Growth Regulation of Wheat Wheat testing is done in 13 cm round plastic pots. The wheat is planted in a mixture of 75 percent soil and 25 percent sand which has been steam pasteurized to control indigenous weed seed and pathogens . Seeds are planted and then covered with approximately 1 cm soil/sand mix and placed on fiber matting in the W'()')1/0110(19 I'CI~/US90/03G7Z
-~2- 205024 greenhouse. The pots are both mist watered and bottom watered until seedlings emerged. After emergence, only bottom watering is done. At the times of treatment, the growth stage is recoi:ded, and pots are removed to a spray hood for treatment. Ttre compound to be applied is placed in a 15 by 125 mm test tube and dissolved in 12 ml of acetone and water. '.t'he compound is sprayed onto the foliage using a hand held Devilbiss spray gun (Model EGA-502). This sprayer emits an extremely fine spray particle and results in maximum coverage of the foliage.
Operating air pressure is 840 gm/cm2. Applications are made at four different rates at each of six growth stages. The growth stages are as follows:
I. one leaf II. three to four leaf, some initial tillering III. three to tour leaf, distinct tillers with two to three leaves IV. five to six leaf, with four to five tillers V. flag leaf present, inflorescence within culm VI. boot stage, inflorescence emerging from culm Results (being an average of all indicated readings) for the compounds of Examples 1 and 16 are set forth in Tables 4 and 5, respectively.

v~o vlioo°°v ncivusvoio3~~7z ~p;~~024-73-EFFECT ON GRAIN WI;IGI~TJ, WEIGHT
INTERNODE LENGT i AND BREI~KING STRENGTH
GRAIN PLANT LENGTlI LENGTH BREAICING
5TREATMENT WEIGHT HEIGHT am cm STRENGTH
kg/ha gm cm INTERNODE INTERNODE gm A B

0 0.62 28.3 24.8 8.6 61.0 2 0.61 31.7 19.9 7.1 66.7 4 0.53 31.5 20.0 7.0 53.9 * Weight necessary to break a 10 cm segment of Internode A.

EFFECT ON i~UriBER OF TILI~)~R:3 PRO UCING GR71IN. GRAIN WEIGIiT
STRAW WEIGHT hND P~N'I' IiEIGiiT
GRAIN STRAW PLANT
RATE TILLER WEIGIiT WEIGHT HEIGHT
kg/ha COUNT gm gm cm 0 16.2 12.1 13.4 23.3 1/2 18.1 12.6 14.7 23.7 1 19.0 12.8 15.2 22.5 2 19.7 1.3.7 15.8 22.9 4 19.2 13.1 15.0 22.9 Effect on Wheat Tillerinct Single soft red winter wheat (Triticum aestivum) seedlings growing in soil in 4 inch R plastic wo ~moono~~ rcriusooin3~,~2 pots are treated with broadcast spray applications of the compound of Example 15. 11t the tune of treatment, the plants are starting to tiller. Most seedlings have one tiller, while a few have two or no tillers. Treatments are repl icated six times ( except 5 times at 3 gm/ha ) . At various times during the course of the study, various parameters are determined: number of flag leaves, number of seed heads and yield measurements. These and other determinations are reported in Table 6. No commercial l0 standard is included, because none is known. The yield increases are attributed to increased tillering (flag leaf counts) and therefore more seed heads per plant.
The high dosage (1,000 gm/1)a tends to delay tillering.

-- -_ -Doaope N~wlwcr Total GrainSced Nubcr Seed p~ Lft.
ANha Flsp (% of control) leaves/Plent Nenda/Plant ~g/Seed -3 6.4 ~ 10,4 10.2 t 27.1 (136)30.4 1.5 t 3.5 4.1 10 6.0 : 8,3 t 8.2 t 2.2 20.7 (104)29.2 1.3 3.1 30 9.0 t 11.7 11.8 t 28.9 (145)28.2 2.4 t 2.7 3.7 2 0 100 7.5 s 13.7 14.0 t 33.5 (168)27.7 1.5 t 2.1 1.7 300 6.0 : 13.3 13.5 t 33.9 (170)28.5 1.4 t 3.3 4.4 1000 3.7 : 15.3 14.T t 35.0 (176)27.9 3.1 ~ 2.6 3.3 Control5.8 s 8.0 ~ 7.3 t 3.4 iD.9 (100)27,0 2.5 3.B

DAT1 57 96 145 (harvest)162 162 2 5 ~ DAT = Deys After Treatment NOTE: Grain uas pooled for each treatment erd weighed 17 days after harvest (162 DAT).
The 3 gm/ho treatment was ed)usted to 6 replicates.

W() 91/0(1()09 1'CT/US90/03G72 ''~ -75-~X71MPLE 1. 0 3 ~f ect on Weed Beets 2 0 3 5 0 2 4 In some areas where sugar beets ( eta vulaaris) are grown, many fields become infested with weed beets which do not form usable roots. These weed beets can also bolt any time during the season thus insuring continuing infestations. No herbicide is selective enough to control weed beets in sugar beets. A possible weed beet management approach would be to prevent seed production by early treatment of flower stalks with wipe-on or recirculating sprayer applications. To this end, three greenhouse studies are attempted and reported in Table 7. Test plants are grown in 5" R plastic pots.
Treatments are applied as directed sprays onto developing flower stalks. Percent reduction is based on fresh weight of surviving floral growth. The compound from Example 1 is prepared as an acetone/water/ surfactant lab formulation. ROUNDUPTN (Monsanto) and A-RESTT" (Eli Lilly) are commercial herbicide and plant growth regulant formulations, respectively.

W() 91/0000') I'Cf/US9(1/03Cr72 TnHZ.$ ~
Percent Reduction of Floral Parts Dosage Compound mg/Plant Test n Test H Test C

Example 1 0.1 1G 100 100 0.3 35 100 100 Roundup" 2.0 (5G)Z 3g ___ 6.0 11 gg ___ 18.0 100 100 --_ 71-RestT~ 0.33 --- --- 21 1.0 ___ '___ 69 3.0 __- __- 92 DAT = Days After Treatment Denotes percent increase &~~ 104 Effect on Maple Seed~i a s Actively glowing seedlings of cer palmatum.
(Japanese cutleaf maple) are sprayed to runoff with aqueous dilutions of the compound of Example 15 and ATRINAL~~ (a commercial formulation by MAAG of dikegulac). Pinched as well as untreated controls are included. All treatments (4 replicates each, recorded 78 days after treatment) are listed in Table 8.

~V() 91/(IU(1(I~1 PCT/US90/03G72 _77-203~~24 Glyoxylate dosages bracket the range from no effect to an excessive effect at the dosages tested.
TA>3LE 8 compound Concentration Hean Number (pPm) Terminals/Plant Example 15 5 1.0 0.0 15 58 2.2 50 9.5 3.0 150 9.8 2.4 500 greater than 14 Artrinal 1500 11.5 2.5 3000 9.0 0.8 Control - ---- 1.0 0.0 Pinched Control ---- 1.3 1.5~

' Two of the four seedlings went dormant after pinching.
l0 EXAMPLE 1n~
effect on Azaleas Rooted single-stem cuttings of azaleas (Rhododendron sp., cv 'Elsi Lee') are transplanted to artificial potting medium in 4 inch round plastic pots.
These cuttings are pinched as they were moved. After growth resumes, these plants are sprayed to run-off using a hand held spray unit. Treatments employ the K salt of Example 15 and dikegulac, a commercial plant growth regulator which is used to induce branching and to 1V0 91 /(10(109 ~Q~~~24 '7a-~'C1~/US9()/03G72 prevent regrowth after pruning. Treatments, based on five replicates of each are listed in Table 9.
Flower bud counts are recorded 122 days after treatment. Glyoxylate treatments induced increases in flower bud numbers.

-- -~ _ ~ concentration Mean Number ' C
om ound ~Ppm) Flower nuds/plants Example 15 10 3.2 1.9 20 8.4 3.1 40 15.8 4.3 80 23.2 5.8 1G0 Partial defoliation, Stunted l0 Dikegulac 1500 5.2 3.5 3000 5.4 2.7 6000 5.2 3.7 Control ---- 3.0 0.7 Pinched Control*

---- 7.2 2.4 * All plants are pinched when potted. The "pinched control" is pinched a second time, when the other plants are sprayed.

_7g_ Effect On Brs~m~hW ci of Cleans 2~, 3 5 0 2 4 In order to determine their effect on branching patterns in plants, compounds were evaluated on Charlevoix ~ limbing beans. Under normal conditions, these plants exhibit strong apical dominance with little or no branching. Plants were grown individually in 4"
diameter pots in the greenhouse, and were treated when the lst trifoliate leaf was expanded (plants l0 approximately 10" tall). Two independent studies were conducted. In the first, compounds were applied at 25 ppm, while in the second the application rate was increased to 100 ppm. In both studies, compounds were sprayed on plants to runoff using a hand-held sprayer.
Compounds were dissolved in a solvent system of 67% water and 3 3 % acetone with 0 . 067 % (v/v ) Tween 2 0 added as a surfactant. For some compounds not soluble in this system, 100% acetone with Tween 20 was used. For each compound, three replicate plants were treated and evaluated. Plants were grown in the greenhouse for an additional 3 weeks before the compounds' activity was evaluated. Results are summarized in Table 10.

1V() ~) 1 /1101)09 I'Ct~/t1S90/03672 EFFECT OF COMPOUNDS (DE~~GNATED ~~~AMpLE NUL~BER) ON
NC NG C G W EATM NT
Rating Code: 0 = No effect l = Slight effect a~ txxf break 2 = Moderate effect a~ bud break aril branching ~ ~ 3 5 n 3 = Strong enhoncement of bud break and brerxhin ;J ~/g Exnple Rate Ncd~ Exa~rte Rate hear, Rstinp t Rating 25 L00 25 l00 !

1 3 3 3.0 27 3 3 3.0 2 3 3 3.0 28 1 3 2.0 3 2 3 2.5 29 0 1 0.5 5 2 3 2.5 30 0 1 0.5 b 2 3 2.5 31 0 1 0.5 7 1 2 1.5 32 i -- 1.0 _ 1 3 2.0 33 2 1 1.5 9 3 1 2.0 ~ 1 1 1.0 10 3 3 3.0 35 2 0 1.0 11 3 3 3.0 3b 1 3 2.0 2 12 1 3 2.0' 38 2 1 1.5 12~ 3 3 3.0 39 2 3 2.5 13 1 3 2.0 40 t 2 1.5 14 2 3 2.5 41 3 3 3.0 15 3 3 3.0 42 3 3 3.0 2 16 1 3 2.0 43 2 1 1.5 17 3 3 3.0 44 2 1 1.5 18 3 3 3.0 45 2 1 1.5 19 0 1 0.5 46 1 1 1.0 0 1 0.5 47 2 1 1.5 21 1 2 1.5 4B 2 i 1.5 22 2 1 1.5 49 2 3 2.5 24 1 1 1.0 50 2 1 1.5 26 1 3 2.0 52 2 1 1.5 1V() 91 /0(1009 ~~~5~24 -°1~
I'C1~/US90/03G72 - ~.~.
E~~'Pi~ Rete Ncen Exwe~~ie R

ete Retinp Rating _ l00 ~

53 Z 1. 5 75 2 1 t . 5 54 1 1 t.0 76 t t 1.0 55 1 1 1.0 T7 2 1 1.5 56 1 1 1. U T8 _ 3 3 3 . 0 57 t 1 1.0 79 3 3 3.0 58 2 0 1.U 81 2 , 1.5 59 2 0 1.0 82 Z t t.5 60 t 1 1.0 83 0 1 0.5 61 1 1 1.0 83 0 t 0.5 62 1 1 1.0 85 1 0 0.5 63 1 3 2.0 ~ 0 t 0.5 t 3 2.0 87 t 0.5 65 3 3 3.0 88 0 1 0.5 t 3 2.0 89 0 1 0.5 67 1 3 2.0 ~ t 0.5 1 1.5 91 1 0 0.5 69 3 1 2.0 92 0 1 0.5 70 2 2 2.0 2 93 3 3 3.0 0 71 1 2 1.5 94 0 t 0.5 72 t 1 t.o 95 o t o.s 3 1 2.0 96 t 0.5 74 2 3 2.5 97 1 3 2.0 All of the compounds ellicited some degree of increased bud break and/or branching in climbing beans.
For most compounds, activity tended to be greater at 100 ppm titan at 25 ppm. In summary, these compounds are effective as branching enhancement agents in beans.

W() 91/(1(1(1(19 1'CI~/US90/()3G72 ~XI,MPLE 107 Fffect vn Size Maintenance o~ ~~vet liedae ~ 0 3 5 0 2 4 Ten compounds were evaluated to determine their efficacy in size maintenance of privet hedge. Potted privet plants were overwintered in a protective cool greenhouse and transferred to a warm greenhouse in early March. Bud break and leaf development were allowed to continue for 1 month until plant height was approximately 30 cm. Because privet hedge plants are commonly trimmed to a desired shape, one-half of the plants were trimmed prior to chemical application. Plants were sprayed to runoff using a hand-toeld sprayer. Compounds were applied at a concentration of 20 ppm in a solvent system of 50%
water, and 50% acetone containing 0.1% (v/v) Triton X-100 as a surfactant. For each treatment, ?. replicate trimmed plants and 2 replicate non-trimmed plants were treated.
Plant height of each plant was recorded on the day of treatment and compared to the plant height at 29 days after treatment. Table 11 shows the net increase in plant height after treatment.

~VU 91/(I(I(IU9 1'Cl~/US90/03(71 TABLE il EFFECT OF CO~?OUNDS O~ HEIGHT CIiJI.NG~]~' OF 2 0 3 5 0 2 4 GOLDEN POET 29 DAyS AFTER TREATMENT
Net change in Examplo ~ plant height ~cm~

Trimmed* Non-Trimmed**
Plants Plants Non-Sprayed Control f3.0 7.0 Sprayed Control 7.0 7.5 1 0.0 -0.5 2 -2.5 -1.5 3 1.5 0.5 9 -1.0 -1.0 -0.5 0.0 41 -1.0 -2.0 42 0.0 2.0 65 -1.0 0.0 15 78 0.5 0.0 79 -0.5 0.0 *Average plant height at time of treatment was 30 cm.
**Average plant height at time of treatment was 40 cm.
Trimmed and non-trimmed plants responded similarly to application of the compounds. Control plants (both non-sprayed and those sprayed with the solvent) grew from 7 to r3.5 cm. In contrast, plant height remained essentially the same in all plants treated with the compounds. Thus, these compounds were quite effective in maintain~.ng plant size both in trimmed and non-trimmed privet hedge plants.

1V() 91/II(I(II19 I'CT/hS90/03C72 Effect on Terminal Elos at on ~f Green Ash ~ ~ 3 5 0 2 4 Ten compounds were applied to green ash seedlings to determine if they could control elongation of terminal buds. Potted green ash seedlings were overwintered in a cool greenhouse and transferred to a warm greenhouse in early March. Wittrin 1 month terminal buds were released and began to grow. Plants were then sprayed to runoff using a hand-held sprayer. Compounds 1.0 were applied at two concentrations, 20 ppm arod 100 ppm, in a solvent system of 50% water, 50% acetone containing 0.1% (v/v) Triton X-100 as a surfactant. For each treatment, 4 replicate plants were treated. Plant height of each plant was recorded on the day of treatment and compared to the plant height at 2a days after treatment.
Table 12 shows the net increase in plant height after treatment.

~
V() 91 /11111)09 I'C1'/US9(1/03G72 -~5- 20 3 5 0 2 4 EFFECT OF COMPOUNDS ON IIEIGJIT CJiI~NGE OF GREEN ASH
SEEDLINGS 28 DAYS AFT'FI~ TREA'~rg'ENT
Net change in Example ~ plant height*

(cm) 2o ppm loo ppm Non-Sprayed 18.3 Control Pinched -Non-Sprayed 11.0 Control Non-pinched Sprayed Control 15 Pinched . ---Sparyed Control 8.5 __ Non-Pinched 1 0.0 _ -0.3 2 -0.3 0.8 . -0.3 0.0 -1.5 15 0.8 0.0 17 0.0 -0.1 41 1.3 0.8 . 0.3 65 0. 5 -0.5 79 0.3 1.5 *Average plant height at time of treatment was 34 cm.
Non-sprayed control plants in which the terminal bud was pinched grew 18.3 cm while non-sprayed non-pinched plants grew 11 cm. Similarly, pinched control plants sprayed with the solvent increased in height 15 cm and non-pinched, non-sprayed plants grew 8.5 cm. In contrast, all compounds tested essentially eliminated terminal bud elongation, regardless of concentration of the applied solution. Thus, these compounds appear to have excellent utility when used to reduce vertical growth of this tree species.
Twenty-three compounds were tested for their l0 utility as turfgrass retardants. Bluegrass, cv Haron and perennial ryegrass, cv Pennfine were planted in 3" sqaure pots in late February. Grass was allowed to grow for 6 weeks before treatment. Grass was cut and fertilized on -a regular basis to provide a thick turf. Just prior to chemical treatment, the bluegrass and ryegrass were trimmed to heights of 20 mm and 15 mm, respectively.
Four replicate pots of each species were treated at two rates, 0.5 kg/ha and 2.0 kg/ha. Compounds were sprayed in 50% acetone, 50% water containing Triton X-100 at 0.1%
(v/v) as a surfactant. Some compounds were sprayed in 100% acetone containing Triton X-100 Plant heights 2 weeks after treatment were recorded and are summarized in Table 13.

W<) 91/00(109 I'Cl'/US90/03G72 _F37~

EFFECT OF COI~POUNUS O~I, P~.~11NT i;EIGHT OF BLUEGRASS AND
RYEGRASS ~g U~yS AFTER TREATMENT' Plant ight He (a~) E s(~9ras s" R rasa r"
l xa~ 0.5 2.0 0.5 2.0 e ! kg/ha kp/ha kg/ha kg~he Non-5 ra ed Control 137.5 .__ 126.3 ---S rayed Control 132.5 --- 130.0 ---Embark 30.3 30.3 50.5 49.8 Limit (2.5 qt/acre) 43.5 --- 53.0 ---I 44.3 40.8 31.8 26.3 1 0 2 49.8 40.5 27.5 26.8 3 39.0 _34.0 33.8 33.3 5 44.0 32.0 30.3 29.0 8 51.3 31.8 ZT.O 30.8 41.3 34.3 30.3 27.8 1 5 10 43.0 34.5 32.3 34.3 11 41.0 38.5 34.8 29.8 33.8 34.8 25.8 26.8 16 47.0 44.0 29.0 29.3 17 39.0 31.8 28.3 27.8 2 0 18 42.8 44.8 28.3 28.3 27 42.8 31.0 3D.5 24.3 36 95.0 81.8 40.5 42.0 39 67.5 44,3 34.8 32.8 41 48.8 39.8 43.8 34.5 2 5 42 117.5 106.3 101.3 85.0 65 47.8 45.8 33.3 32.8 68.3 _51.5 58.8 38.8 74 35.0 33.3 35.3 32.0 -ee-Il~nt Nel t (v) lluepr~s~ It rw"

Example 1 0.5 2.0 0.5 2.0 k1/hs k1/h~ k1/h~ k9/h~
i 33.fi 33.0 36.0 33.ls T9 45.1! 52.5 G0.0 45.8 93 34.0 33.0 it.3 31.0 ~Averspe plsnt height et time of trestment ws~ 20 ~.
~~Averspe plant height et tine o! treet~nent wse 15 urn.
Both bluegrass and ryegrass controls grew to a total height of approximately 130 mm (net growth of 115 mmj during the two week preiod after treatment. The commercial standards, Limit~ and Embark~ reduced total l0 plant height to approximately 30 to 50 mm, depending upon rate and species. Similar plant height reductions were _ observed in many of the compounds tested. Several compounds, however, showed little or no activity. In addition, responses also varied between the two species, with ryegrass growth appearing to be more susceptible to chemical retardation, particularly at low rates. In summary, turf retardant activity of this class of chemistry appears to be at least comparable to the currently available commercial standards.
.B

Claims (5)

CLAIMS:

1. A method of inhibiting the growth of undesirable vegetation which comprises contacting said vegetation's locus with a herbicidally effective amount of a compound having the formula wherein:
A is COOR, COSR, CSNH2, CN or, together with one of B, -C(=0)0-;
R is H, Na, K, di(C1-C4)alkylammonium, diethanolammonium, C1-C8 alkyl, C2-C8 alkoxyalkyl, cyclohexyl, tetrahydrofurfuryl or dimethyldioxolanylmethyl;
Z is H or CH3;
B is H or, together with A, -C(=0)0-;
Y is H, C1-C4 alkyl or alkoxy, CF3 or X; and X is F, Cl or Br, provided that where more than one of Y is other than H on either ring they must be in the 3, 4, 8 and/or 9 positions and, where Y is in the 1, 2, 10 or positions on the rings, no more than one of Y is other than H and that one Y
is CH3.

2. A method as in claim 1 wherein Y, B and Z are all H.

3. A method as in claim 1 wherein B and Z are all H.

4. A method as in claim 1 wherein Y and Z are all H.

5. A method as in claim 1 wherein Y at the 1, 2, 10 and 11 positions, B
and Z are all H.