AU511199B2

AU511199B2 - Herbicidal 4-substituted 1, 3-dioxanes

Info

Publication number: AU511199B2
Application number: AU27867/77A
Authority: AU
Inventors: M. J Konz
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 1976-08-31
Filing date: 1977-08-12
Publication date: 1980-07-31
Also published as: RO74637A; AR219717A1; IN146343B; FR2363566A1; CH628627A5; FR2363566B1; AU2786777A; LU78058A1; IE45464B1; DK384177A; DE2739067A1; BR7705818A; ES461972A1; IE45464L; JPS5337671A; SU741777A3; GB1557103A; IT1086066B; CA1101424A; IL52701A

Description

Av

(Notc: This i~sa comprehensive form, and parts inappropriate to a particular applica Australian Patent Attorney. No legalisation is necessary).

F -4- 17.

CONVENTION OR, NON- *CON mgvPATENT Of tPA'

afnsoriefoll nameis) of applicani(s)FM we 0 ~lWe 1 CO P R TI ON *5* 0

SO .5 S S %T-VAUJ aOF SS S t.'1;AJHM F 1 RTY 0D0LLA NTY 1 0LLA Oa~CFFICM

Insert raull add essleni .1 Street. .ark

.1 Philadelphia, Pennsylvania 19103, U.S.A. 0

Delete whirnever hereby apply for the grant of a pate ntj-p~i en t of adi~ for an invention entitled is i"'applicable

Insert title f (d)...HERBICIDAL 1 -DIOXANES invention

which is described in the acdompanying previsitii4-j-complete specificiation.

1/ We-requost that the-a t~yb-r~ne.a~.aptnof.adto to

c) the patent applied for on application No. i h aeo patent-N nte aeo Delete entirely if inapplieable

We request that the term of the, patent of addition be the same as t a the patent for the

a-Ir I, ta4.a+%.+h-y1- 2

I'his application is a Convention application and is based on the following application or

Applications for a patent or patents or similar protection made in the following country or

Deleie entirel it ,ountries on the following date or dates: conve nton priority NOT claimed 181 Insert number of first batie applicaiin (f) N o in on (i.w .J 0 l9..

Wh Insertcountry is No.(g 8119.1 in (h U.S. nhIch first bausic application was miade NO. in on .7. (0 Insertdate oil fiest basic applicaion N o. in on 19

My/ Our address for service is care of CLEMENT HACK CO., Patent Attorneys, 140

William Street, Melbourne, Victoria, 3000, Australia. ill Insert date Dated this 12TH day of AUGUST 1977

FMC

fbI Signatuels) of a pplicanitnl) Wfe company, to be eXecued in a marine, CLEMENT HACK CO. binding on the Company according to its Articles of Association or tbe laws of the countr) Ill Fieel of toe Company (if

To: The Commissioner of Patents

-6--et T( P. 1-1-1 Ac An lAn qt;l~e, Mi-lhhuuurrt Vi,'teiir;i 3000 A ustralia

11f Australia Patent Declaration Form

Forms 7 and 8

AUSTRALIA

Patents',Act 1952

DECLARATION IN SUPPORT OF A CONVENTION OR NON-CONVENTION APPLICATION FOR A PATENT OR PATENT OF ADDITION

27 8 67 m Name(s) of In support of the application made by FMC CORPORATION Applicant(s) 27867/77 Title for a patent for an invention entitled IEPRRTTnhaT. 1 nTnAM''C 00 Nali4 and I/WB, CHARLES CLARENCE FELLOWS, of 2000 Market Street, addless(es) Philadelphia, Pennsylvania 19103, United States of America of pe-Atn (s) makig declerMtion do solemnly and sincerely declare as follows:-

i. i ax^iX$^p am/Xif authorised by the abovementioned applicant 0 6 6 to make this declaration on its behalf. go e 0 6 2. The basic application(s) as defined by Section 141 of the Act was/were made in the following country or countries on the following date(s) by the following applicant(s) namely:- Counrl, filing data!and name in U.S.A. on August 31 19 76 of Applicant(s) by MARVIN JOSEPH KONZ for, t or in U.S.A. on June jU 9_ 2 eachb,§ic by MARvTN -JOSEPH _KONZ application

@0 3. The said basic application(s) was/were the first 0 o* application(s) made in a Convention country in respect of the invention the subject of the applic Lion. Name(s) and 4. The actual inventor(s) of the said invention is/are address (es) MARVIN JOSEPH KONZ, of 7109 Fieldcrest Drive, of the or each actual .Lporprt, New York 140.94, U.ite_d_States of America a citizen of the UnitedStates of America inventor See reverse 5. The facts upon which th? applicant(s) is/are entitled side of this to make this application are as follows:- form for The....said. FMvLC RORATIONis the assignee of the said guidance in MARVIN -TSElP.LLMRK completing this part

Philadelphia DECLARED atPennsylvani,UI.S this 28th day of February 19 FMC COPOTI N

By N CHARLES CLAR CE FELLOWS Authorized Official

This form may be completed and filed after the filing of a patent application but the form must not be signed until after it has been completely filled in as indicated by the marginal notes. The place and date of signing must be filled in. Company stamps or

(11) AU-Bl-27, 867/77

(12) PATENT SPECIFICATION ABRIDGEMENT (19) AU

(21) 27,867/-77 511,199 (22) 12.8.77 (23) 12,8.77 (24) 31.8.76 (31) 719,311 (32) 31.8.76 (33) US 811,918 1'.6.77 us (43) 15.2.79 (44) 31.7.80 (51)2 C07D 319/06 C07D 319/'08 C07D 407/12 C07D 405/12 C07D 409/12 A01N 9/24 C07C 43/20 C07D 301/14 C07C 31/18 (54) Herbicidal 4-substituted 1,3-dioxanes (71) FMC Corporation (72) Konz, M. J. (74) HA (56) 56,068/73 476,788 09.62-20 87.16 09.62-25 3.1.5 46,650/72 473,478 09.62-20 87.16 46,132/72 480,294 09.62-20 87.16 09.17 09.62-1 09.18 (57) Claim 1. A compound of the formula:

R6 0 CR 0 C 2 Rr

C ZC R2 a 0-CHR

characterized in that R2is hryd.,7ogen, alkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, or phenyl; Ris hydrogen; and R aand R2taken together may represent a divalent polymethylene radical of 2 to 6 carbon atoms, and so form a spiro structure; /2

28-9

4F

(11) AU-B1-27,867/77 -2-

R is alkyl, haloalkyl, or cyanoalkyl; 5 R is hydrogen or alkyl; 6 R is hydrogen, alkyl, haloalkyl, or cyanoalkyl; Rr is phenyl, furyl, pyridyl, thienyl, or phenyl with one or two substituents selected from the group consisting of chloro, fluoro, and methyl; and in that -OCH 2 Rr bears a cis-relationship to R other than hydrogen.

To: The Commissioner of Patents -Il

ii 4r~'p ri ~flJ;1~,- 1 MPIhivrnp Virtoria 1000, Australia

COMMONWEALTH OF AUSTRALIA

PATENTS ACT 1952-69 Af COMPLETE SPECIFICATION (OR IG INAL)

FOR OFFICE USE: Appi cation Number Class I t. Class Lodged

Complete Specification Lodged U e~

Accepted: Published: P~riority

R@.elated Art: see

Name of Applicant(s) FMC CORPORATION

0*

,,0 Address of Applicant(s) 2000 Market Street 0 0 4,e Philadelphia, Pennsylvania 1.9103, U.S.A.

00 p p @0 Actual Inventor(s) Marvin Joseph KONZ 000... o

Address for Service CLEMENT HACK CO. A4*-6e4i-Treet lU-Ac Melbourne, Victoria, 3000 AusA ralia.

Complete Specification for the invention entitled: "HERBICIDAL 1 ,3-DIOXANES"I

The following statement is a full description of this invention, including the best method of performing it known tq me/us: trtMOCtF(M.PTT.Ut -1 application but the form must not be signed until after it has been completely filled in as indicated by the marginal notes. The place and date of signing must be filled in. Company stamps or

FMC 4308

This invention describes novel herbicidal compounds,

new herbicidal compositions, and new methods for pre-

venting and destroying undesired plant growth by pre- 0. emergence and postemergence application of said new and

*e useful herbicidal compositions to the locus where control

is desired. Effective control of the growth of a variety

of grassy plant species is obtained. At levels of pre-

emergence application which prevent growth of grasses,

the compounds of the invention show selectivity favorable 0*

"10 to soybeans, cotton, wheat, sugarbeets, tomato, and pea-

nuts. The herbicidal compositions may be applied and

utilized by commonly accepted methods.

Herbicidal 1,3-dioxanes carrying substituents other

than hydrogen in the 2- and 5-positions of the dioxane

ring have been described in the patent literature, Also

described are 5-substituted-l,3-dioxanes with no 2-sub-

stituent other than hydrogen. In the previously disclosed

1,3-dioxanes, the carbons in the 4-position and the 6-posi-

tion carried only hydrogen.

-i -i i i m d~l L EL~--

It has now been found that by introducing a substi-

tuent, for example a lower alkyl group, in the 4-position

or in the 4- and the 6-positions of the previously known

herbicidal 1,3-dio ansc, herbicidal activity is retained

and may be enhanced. The new class of 1,3-dioxanes sub-

stituted in the 4-position has shown an unexpected

increase in herbicidal activity over the prior art

dioxanes with no substitution in the 4-position.

The novel herbicidal compounds in accordance with

10 this invention have the following general formula (in which

the numbering of the R-substituent signals the numbering

S of the positions on the 1,3-dioxane ring): OCH2 Rr X

RS R6 R 6

0 R e 4

09 R2 3

R2

wherein R 2 is hydrogen, alkyl, haloalkyl, cyanoalkyl, 2' 2 alkoxyalkyl, or phenyl; R is hydrogen, and R and R taken together may represent a divalent polymethylene

radical of 2 to 6 carbon atoms, and so form a spiroalkane; 4 R is alkyl, haloalkyl, cyanoalkyl, or alkoxyalkyl, and

R is hydrogen; R 5 is hydrogen or alkyl; R 6 is hydrogen,

alkyl, haloalkyl, cyanoalkyl, or alkoxyalkyl, and R is hydrogen; R r is phenyl, furyl, pyridyl or thienyl; X is chloro, fluoro, or methyl; and n is 0, 1, or 2.

In preferred compounds of this general formula, an

-2-

m I alkyl component in an R 2 R or R substituent contains 1 to 4 carbon atoms, and especially preferred are compounds in which R 2 is hydrogen, methyl, ethyl, propyl, isopropyl, chloromethyl, bromomethyl, cyanomethyl, 2-cyanoethyl, and methoxymethyl; R2'is hydrogen; R is methyl, ethyl, and propyl; 5 is hydrogen; and R 6 is hydrogen, methyl, ethyl, and propyl; Rr is phenyl; n is 0, and 1 with X in the 2-position of the phenyl ring, and 2 with X in the

S 2- and 6-positions of the phenyl ring.

It is seen that while R 4 and R will always be hydro- .4 5 6 gen, and R will always be alkyl, R5 and R may each be

independently hydrogen or alkyl. This is seen to give rise to four possible combinations, as follows: 4 5 6 Theoretical No. R R R Stereoisomers alkyl H H 4 alkyl alkyl H 4

alkvl H alkyl 6

alkyl alkyl alkyl 6 2 When R is taken as a reference group, the benzyl-

oxy group (or furylmethc'xy, pyridylmethoxy, or thienyl-

methoxy group) in the 5-position may be oriented axially

(cis) or equatorially (trans). When R 4 and R6 are alkyl they may also be oriented axially or equatorially to the

reference group. The number of conceivable stereoisomers

is substantially greater than the number of possible sub-

stitutions. For above there are four conceivable stereoisomers, for there are four conceivable stereo- isomers, for there are six conceivable stereoisomers, and for there are six conceivable stereoisomers.

Although there are 20 conceivable stereoisomers among the

four substitution isomers and not all

will be obtainable because of spatial restrictions or

equilibria favoring an alternate orientation.

Optical isomers are also possible, as there are a..

asymmetric centers in the dioxane molecules.

S0 Herbicidally preferred are compounds in which the a e' benzyloxy group (or furylmethoxy, pyridylmethoxy, or

thienylmethoxy group) bears a cis-relationship to the

2-substituent. Especially preferred herbicidally are

compounds in which the 4-substituent and the

oxy group both bear a cis-relationship to the 2-sub-

*aa stituent.

The stereochemistry of the derivatives of

1,3-dioxane has been discussed in the scientific literature

a [see, for example, Baggett et al, J. Chem. Soc. 2574(1960)

and Dobinson and Foster, J. Chem. Soc. 2338(1961)]. As

Sa pointed out there, a cis-relationship between the

stituent and the 2-substituent occurs when the

stituent is in an axial position and the 2-substituent is

in an equatorial position. Much information concerning the

structures involved can be obtained from nuclear magnetic

resonance spectra. The patent literature contains a dis-

cussion of nmr analysis of 2,5-dialkyl-5-hydroxy-l,3-

dioxanes. [See also, Gelas, Bull. Soc. Chim. France

1975 1237-1242, for a discussion of nmr analysis of

an isomeric mixture of 2,4-dimethyl-5-hydroxy-l,3-

dioxanes.]

Preparation of the compounds of the invention and of

intermediates from which they are prepared is described

below. In the descriptions which follow, all temperatures

are in degrees centigrade. All reduced pressures not

otherwise designated are pressures normally attainable

using a water aspirator.

The isomerization of hydroxylated dioxolanes and

to dioxanes by selective distillation in acid medium has been

described by J. Gelas, Bull. Soc. Chim. France 1970 (11), 4041-4046. This method has been used to prepare an alco-

hol precursor to the compounds of this invention, r-2-

ethyl-c-5-hydroxy--4-methyl-l,3-dioxane. Gelas (at Bull.

Soc. Chim. France 1975 1228-1236) has described the

synthesis of a mixture of erythro and threo 1,2,3-butane-

triols from a mixture of cis and trans crotyl alcohols,

and its subsequent reaction with acetaldehyde to give an °20 isomeric mixture of dioxolanes and 2,4-dimethyl-5-hydroxy-

1,3-dioxanes. These reactions are set forth in the

following schema:

R H KMnO, R4 OH OH H C=C H2 0 C-C H CHaOH Catalyst H trans-2-alken-l-ol 50 threo-1,2,3-alkanetriol (I) OH H

1)Condensation& 0 2)Distillation p-toluenesul_ 0 R fonic acid H H R H

Synthesis of Intermediates

threo-1,2,3-Butanetriol

A stirred mixture of 12.5 g of trans-2-buten-l-ol and 0.5 g of 2,3,11,12-dicyclohexyl-l,4,7,,1,13,16-hexaoxa-

cyclooctadecane ("dicyclohexyl-18-crown-6") in 125 ml of

water was cooled to 50 and maintained near 5° for one-half

hour during addition of 32.88 g of potassium permanganate.

Upon completion of the addition the temperature of the mix-

ture was allowed to rise to ambient temperature, at which

the mixture was stirred for 2.5 hours. The reaction mix-

ture was filtered and the filtrate was evaporated under

reduced pressure until a viscous liquid residue remained.

The residue was distilled using a short-path distillation

system, yielding 6.13 g of clear, viscous threo-1,2,3-

butanetriol; bp 97-990/0.02-0.025 mm. The ir and nmr

spectra were consistent with the assigned structure.

Analyses calc'd for C4Hi003: C 45.27; H 9.50;

Found: C 45.54; H 9.58.

'Wdr .0

A. r-2-Ethyl-c-5-hydroxy--4-methyl-1,3-dioxane

A solution of 23.26 g of propionaldehyde, 42.56 g of

threo-1,2,3-butanetriol, and 0.93 g of p-toluenesulfonic

acid in 750 ml of hexane was stirred at ambient temperature

for 1 to 2 hours, and maintained at reflux temperature for

16 hours, by which time 6.40 ml of water had been

azeotropically distilled from the mixture (of a total of

7.23 ml, theoretically obtainable by acetalization with

the triol). The reaction mixture was cooled to ambient

temperature and an additional 3.0 g of propionaldehyde

was added, and the mixture was heated under reflux for two

hours, during which the remainder of the expected water was

azeotropically distilled. The reaction mixture was cooled

and washed with three 75-ml portions of saturated sodium

bicarbonate solution and four 75-ml portions of saturated

sodium chloride solution. The organic layer was dried

with sodium sulfate aid filtered; and the filtrate was

evaporated under reduced pressure, yielding 34.76 g of

yellow liquid. The sodium bicarbonate and sodium chloride

wash solutions were extracted thrice with 200-ml portions

of diethyl ether, and the combined ether layers were washed

twice with 75-ml portions of saturated sodium chloride

solution, dried with sodium sulfate, and filtered. The

filtrate was evaporated under reduced pressure, yielding

22.88 g of yellow liquid. The two portions of yellow

liquid were analyzed by gas chromatography and were found

to resemble each other. They were combined, mixed with

0.93 g of p-toluenesulfonic acid and distilled under

Ipl8~ IL

reduced pressure. Six fractions (A to F) were collected

and analyzed by gas chromatography. Fraction F and the pot

residue were combined and further distilled, yielding four

fractions which were analyzed by gas chroma-

tography also. A sample of fraction D was submitted for

elemental analysis.

Analyses calc'd for C7H1403: C 57.51; H 9.65;

Found: C 57.80; H 9.94.

Fractions C, D, E, G, and H were combined to give

0 31.36 g of r-2-ethyl-c-5-hydroxy-c-4-methyl-l,3-dioxane;

bp 79-810/15-17 mm.

"Using parallel methods, starting with the appropriate

alkanetriol and aldehyde, there were also prepared:

B. c-5-hydroxy-r-2-isopropyl-c-4-nethyl-l,3-dioxane,

bp 72-750/12 mm; C. r-2-ethyl-c-5-hydroxy-c-4-propyl-

:1,3-dioxane, bp 340/0.025 mm; D.

c-4-isopropyl-l,3-dioxane, bp 42.5°-450/0.35-0.4 mm;

E. c-5-hydroxy-r-2-c-4-dimethyl-l,3-dioxane, bp

54-55/3.75 mm; F. c-5-hydroxy-c-4-methyl-r-2-propyl-

20 1,3-dioxane, bp 450/0.5 mm; and G. r-2-tert-butyl-

c-5-hydroxy-c-4-methyl-l,3-dioxane, mp 53.5-54.5°.

erythro-1,2,3-Butanetriol

To a stirred mixture of 100 g of crotyl alcohol in

S00 ml of p-dioxane and 450 ml of water was gradually

added 188.7 g of 30% hydrogen peroxide (56.6 g H202);

this was followed by the addition of 2.82 g of tungstic

oxide (WO3 catalyst. Upon completion of the addition

**flBBffir- ""aaB" L-

the reaction mixture was stirred at ambient temperature

for one hour, at 350 for 16 hours, at 450 for 8 hours, then

at 400 for 16 hours. The reaction mixture was cooled to

ambient temperature and tested with potassium iodide paper

for excess peroxide; the test was negative. The reaction

mixture was filtered through a diatomaceous earth filter to

remove catalyst. The filtrate was neutralized with aqueous

2N sodium hydroxide, and evaporated under reduced pressure *9*

to a residue. The residue was taken up in 800 ml of

0 methanol and dried with sodium sulfate and magnesium a S" sulfate. The mixture was filtered through a diatomaceous

earth filter and the filtrate evaporated under reduced 0 pressure to a residue. The residue was distilled using

a short-path distilling system to give 110.75 g of

erythro-l,2,3-butanetriol; bp 970/0.03 mm.

Analyses calc'd for C H 003: C 45.27; H 9.50;

Found: C 44.98; H 9.29. a.

H. r-2-Ethyl-t-5-hydroxy-c-4-methyl-l,3-dioxane

The dioxolane precursor to this compound was pre-

"O0 pared in the manner of previous 5-hydroxy compounds,

using 50.00 g of erythro-1,2,3-butanetriol, 27.4 g of

propionaldehyde, and 0.75 g of R-toluenesulfonic acid in

255 ml of hexane. Tne crude reaction mixture was distilled

in nineteen fractions to give a mixture of dioxolanes; bp

58-76.80/2.15-3.40 mm. Fractions 3-15 were combined and

redistilled in four fractions to give a mixture of dioxo-

lanes, predominately cis-2-ethyl-4-(erythro-l-hydroxy-

ethyl)-l,3-dioxolane; bp 53-67°/2.5 mm. A sample of 8.80 g of fraction four of this distillation (bp 670/2.5 mm,

65.8% in cis-2-ethyl-4-(erythro-l-hydroxyethyl)-l,3-

dioxolane by gas chromatographic analysis) was combined

with 0.1 g of p-tolvanesulfonic acid and placed in a

refrigerator for 6 days, in an effort to cause equili-

bration to r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-dioxane.

After this time the 8.80 g sample was taken up in 150 ml

of diethyl ether. The ether layer was washed with three

portions of 50 ml each of an aqueous solution saturated with sodium bicarbonate, then with three portions of

S" ml each of an aqueous solution saturated with sodium

S" chloride. The ether layer was dried with sodium sulfate

and filtered. The filtrate was evaporated under reduced

pressure to a residue that was 86.8% in

hydroxy-c-4-methyl-l,3-dioxane (by gas chromatographic

analysis). The crude residue was distilled in five

fractions to give a mixture of dioxolanes and dioxanes; Sbp 87-1040/18-20 mm. It was felt that a trace of acid in

the distillation vessel caused re-equilibration. The

fractions were combined and 0.1 g of p-toluenesulfonic

acid was added. Equilibration took place in a refrigerator

during 8 days. After this time the equilibration mixture

was taken up in 150 ml of diethyl ether and washed vith

three portions of 50 ml each of an aqueous solution

saturated with potassium carbonate, then three portions of

ml each of an aqueous solution saturated with sodium

chloride. The ether layer was dried with sodium sulfate

and filtered. The filtrate was evaporated under reduced

i'i i Ii

-L1_ L

pressure to a residue of 8.65 g that was 82.7% (GC analysis)

in r-2-ethyl-t-5-hydroxy-c-4-methyl-l,3-dioxane. The crude

residue was distilled from a vessel containing 0.05 g of

sodium hydroxide using a spinning band distilling system to

obtain 8 7 LfteenL fracions, bp -u101 mm, Fractions

9-15 were combined to give 2.48 g of

c-4-methyl-l,3-dioxane; bp 100-101°/12-13 mm, 93-95% pure

by gas chromatographic analysis. The nmr spectrum was

consistent with the assigned structure. ""I0 Analyses calc'd for C7H1403: C 57.51; H 9.65;

Found: C 57.42; H 9.90.

Mixture of erythro- and threo-3-Methyl- 2,3,4-pentanetriol A mixture of 75.4 g of 3-methyl-penten-2-ol and

91.44 g of 35% hydrogen peroxide (32.00 g H 2 0 2 in 500 ml of

water was stirred for one hour during addition of 1.8 g of

tungstic oxide (W0 3 catalyst. The mixture was maintained

at reflux temperature for approximately 48 hours. It was

tested for unreacted hydrogen peroxide, and the excess was

20 removed with 6.30 g sodium sulfite in 50 ml water. The solution was filtered, and concentrated under reduced pres-

sure to a residual 62.9 g of reddish-yellow dispersion of

solid in viscous liquid. The material was dissolved in

methanol and the solution filtered. The filtrate was con-

centrated under reduced pressure to a residual 60.45 g of

dark brown viscous liquid. Due to the viscosity of the

liquid, stable pressures were difficult to obtain, however

35.0 g of erythro- and threo-3-methyl-2,3,4-pentanetriol, bp 85-901/.09-.12 mm were collected.

J. r-2-Ethyl-c-5-hydroxy-tL-4, t-5. c-6-trimethyl- 1,3-dioxane and r-2-ethyl-t-5-_HYdrx---,c5 c-6-trimethyl-1.,3-dioxane In mi-ue ith dioxolanes

This mixture was prepared in the manner of previous

hydroxydioxanes, using 35.0 g of a mixture of erythro- and

thr(.o-3-miethyl-2,3,4-pentanetriol, 15.14 g of propion- 9 S.. aldehyde, and 0.49 g of p-toluenesulfonic acid in 200 ml 4

of hexane. The crude reaction mixture was distilled 0 4 *0S4

9 U. 5 (distillation A) under reduced pressure, using a spinning 9 9~

band distilling column, to give in eight fractions 37.3 g A *9* 4

49 U of distillate; bp 30-650/2.75-3.30 mm. Each fraction U was subjected to gas chromatographic analysis; and

fractions were found to be mixtures of cis- and trans- 04 9 hydroxy-l ,3-dioxanes and dioxolanes. 44u

.9 4* 199 Fractions 1-4, bp 49.5-65'/2.90-3.30 mm, were com-

5. bined and redistilled (distillation B) in six fractions to 4 9 9 49

give 14.1 g of distillate; bp 35-56.5*/2.8O-3.05 mm. Gas

20 chromatographic analysis of each fraction indicated frac- 49 9 44

tions 1-4 were predominately cis-hydroxy-1.3-dioxane and 499949 4 di1 oxolane, and fractions 5,6 and the distillation vessel

residue were predominately trans-hydroxy-l,3-dioxane and

dioxolane. Fraction 4, bp 35-55o/2.95-3.00 mm, was

redistilled (distillation C) to give an analytical sample

of cis-hydroxy-l,3-dioxane and dioxolane.

Analyses calc'd for C 9H 180 3 C 62.04; H 10.4 1;

Foind: C 62.29; H 10.70.

-1 2-

~IP~--~CI

Fractions 1,5,6, and the distillation vessel residue

from distillation B and Fractions 5-8 from distillation A

were combined and redistilled (distillation D) in ten

fractions to give 27.3 g of distillate bp 35-650/2.9-

3.1 mm. Fraction 2, by gas chromatographic analysis, was

88,1% r-2-ethyl-c-5-hydroxy, t-4, t-5, c-6-trimethyl-

1,3-dioxane and what is believed to be 2-ethyl-4,5-

dimethyl-4-(l-hydroxyethyl)-1,3-dioxolane; bp

.45-490/3.0 mm. The weight of this fraction was 5.56 g.

9- 10 2-l(l-Hydroxy-l-methyl)ethylj-2-methyl- o oxirane

in A solution of 46.7 g of 2,3-dimethyl-3-buten-2-ol

in 602 ml of chloroform was cooled to 0-50 in a dry ice-

acetone bath. To this was added dropwise, during 4 hours,

a solution of 96.5 g of m-chloroperoxybenzoic acid (113.5 g

S* of 85%) in 966 ml of chloroform. The reaction mixture temperature was maintained at 0-50 throughout the addition.

Upon complete addition, the reaction mixture was allowed

to warm to ambient temperature where it was stirred for

20 18 hours. To the reaction mixture was slowly added a

solution of 11.8 g of sodium sulfite in a minimum amount 4

of water. The reaction mixture was tested for peroxides

using wet acidic sodium iodide-starch paper; there were

no peroxides present. Concentration of the reaction

mixture to below one-half the original volume resulted in

precipitation of benzoic acid from the reaction mixture.

The benzoic acid was removed by filtration. The con-

centration, precipitation, and filtration was repeated

several times until at the last concentration only a small amount of precipitated benzoic acid was collected. There remained 16.6 g of residual yellow liquid, from which on standing a white solid crystallized. The liquid portion was decanted off and the solid was washed with diethyl ether. The ether wash was added to the liquid portion.

The white solid had a melting point of 116-1180 and

decomposed explosively at 170-180°. The liquid portion

was distilled using a Vigreux column, to give 9.32 g of

2- [(l-hydroxy-l-methyl)ethyl]-2-methyloxirane; bp 35-650/15-20 mm. The nmr spectrum was consistent with the

assigned structure.

2,3-Dimethyl-l,2,3-butanetriol

A mixture of 8.73 g of 2-[(l-hydroxy-l-methyl)ethyl]-

2-methyloxirane, 7 drops of concentrated sulfuric acid,

ml of p-dioxane, and 100 ml of water was heated at

during 16 hours. The reaction mixture was made neutral to

phenolphthalein indicator, using sodium hydroxide solution.

The mixture was evaporated under reduced pressure to a

viscous cloudy liquid. The liquid was dissolved in ethanol

.20 and filtered. The filtrate was evaporated under reduced

pressure to give 9.82 g of viscous residual oil. The oil

was distilled, using a short-path distilling column, to

give 8.16 g of 2,3-dimethyl-l,2,3-butanetriol; bp

85-940/0.02 mm. The nmr spectrum was consistent with the

assigned structure.

K. r-2-Ethyl-c-5-hydroxy-c-4,t-4,t-5-trimethyl- 1,3-dioxane

This compound was prepared in the manner of previous rr~l* -rr hydroxydioxanes, using 7.76 g of 2,3-dimethyl-l,2,3- butanetriol, 3.35 g of propionaldehyde, and 0.13 g of p-toluenesulfonic acid in 100 ml of hexane. The crude product was distilled under reduced pressure to give

2.12 g of r-2-ethyl-c-5-hydroxy-c-4,t-4,t-5-trimethyl-l,3-

dioxane; bp 60.5-62.50/1.0-3.5 mm. The nmr spectrum was

consistent with the assigned structure.

Analyses calc'd for C H1803: C 62.04,; H 10.41;

'so Found: C 61.75; H 10.49.

S0 Previously illustrated methods were used to prepare:

L. r-2,c-4-diethyl-c-5-hydroxy-l,3-dioxane, bp 440/0.5 mm;

M. c-4-ethyl-c-5-hydroxy-r-2-methyl-1,3-dioxane, bp 360/0.65 mm; N. c-4-ethyl-c-5-hydroxy-r-2-isopropy.-

1,3-dioxane, bp 390/0.5 mm.

P. threo-2-(2-Methylbenzyloxy)-l,3-butanediol

A sblution of 53.9 g of r-2-ethyl-c-4-methyl-c-5-

(2-methylbenzyloxy)-1,3-dioxane (the compound of Example

II) and 113.2 ml of aqueous 0.75% hydrochloric acid in

226 ml of absolute ethanol was maintained at 600 for

24 hours, after which 244 ml of azeotrope was removed

by distillation; bp 70-830. The residue was neutral-

ized with approximately 12 ml of an aqueous solution

in sodium hydroxide, the mixture was taken up in 1500 ml

of ethyl acetate, and the combination was placed in a

separatory funnel. To the funnel was added approximately ly

100 g of sodium chloride and the mixture was shaken well.

The organic layer was removed and dried with sodium sul-

fate, and then filtered. The filtrate was concentrated

under reduced pressure to a residue, and the residue was

distilled under reduced pressure to give in seven fractions

41.10 g of threo-2-(2-methyylbenzyloxy)-,3-butanediol; bp

121-122°/0.008 mm; ir and nmr spectra were consistent with

the assigned structure.

Q. 2-Methyl-2-(2-methylbenzyloxy)-l,3-propanediol

This compound was prepared in the manner of Inter-

"mediate P, using 250.00 g of r-2-isopropyl-5-methyl-c-5-

(2-methylbenzyloxy)-1,3-dioxane and 500 ml of aqueous

0.75% hydrochloric acid in 1000 ml of ethanol. The crude

reaction product was recrystallized from hexane/chloroform

(50/50) to give 142.60 g of white, crystalline 2-methyl-

2-(2-methylbenzyloxy)-1,3-propanediol; mp 90-91 0 C; nmr spectrum was consistent with the assigned structure. "0 Mixture of dl and meso-2,3,4-pentanetriols

A stirred mixture of 10 g of cis-3-penten-2-ol and 0.12 g of tungstic oxide in 128 ml of water was maintained

at ambient temperature during addition of 20.4 g of

hydrogen peroxide. Upon completing addition, the reaction

mixture was stirred at 600 for 18 hours. The pH of the

filtered reaction mixture was brought to 7-7.5 with aqueous

sodium hydroxide. Excess peroxide was destroyed with an aqucdis. oolution saturated with sodium sulfite. Water was removed from the reaction mixture by heating under reduced pressure. The oily residual solid was taken up in 250 ml of methanol and stirred. The mixture was fil- tered to remove salts. The filtrate was evaporated under reduced pressure to a residual oil. The oil was distilled under reduced pressure using a short path distillation system to give 6.5 g of a mixture of dl and meso-2,3,4- pentanetriols; bp 92-960/0.33 mm. "i' 0 trans-4-(threo-l-Hydroxyethyl)-22,25-tri- methyl-l,3-dioxolane

This compound was prepared in the manner of Inter-

mediate A, using 142.6 g of a mixture of dl and meso-

2,3,4-pentanetriols, 99.1 g of acetone, and 3.4 g of

P-toluenesulfonic acid. Ten g of crude product from two previous reactions were added to the crude product

from this reaction to give a total of 171.8 g of

material. This combination was distilled under reduced

pressure to give in fourteen fractions 94.4 g of trans-

20 4 -(threo-l-hydroxyethyl)-2,2,5-trimethyl-1,3-dioxolane;

bp 62-62.5°/4.7 mm.

meso-2,3,4-Pentanetriol

This compound was prepared in the manner of Inter-

mediate P, using 84.4 g of trans-4-(threo-l-hydroxyethyl)-

2,2,5-trimethyl-l,3-dioxolane, and 278.9 ml of an aqueous

0.75% hydrochloric acid solution in 560 ml of absolute

ethanol. The crude reaction product was distilled under

reduced pressure using a short path distillation system

to give in one fraction 59.2 g of meso-2 3, 4-pentnet:ril.

The nmr spectrum was consistent with the assigned struc-

ture.

Analyses calc'd for C5H1203: C 49.99; H 10.07;

SFound: C 49.70; H 9.91,

SR. r-2-Ethyl-c-5-hydroxy-c-4, c-6-dimethyl-l,3- dioxane S. This compound was prepared in the manner of Inter-

mediate A using 55.9 g of meso-2,3,4-pentanetriol, 41.1 g

of propionaldehyde, and 1.3 g of p-toluenesulfonic acid

in 400 ml of dry hexane. The crude reaction product was

distilled under reduced pressure to give in eighteen fractions 30.6 g of r-2-ethyl-c-5-hydroxy-c-4, c-6-

S. dimethyl-1,3-dioxane; bp 76.5-770/15 mm; ir and nmr

spectra were consistent with the assigned structure.

Analyses calc'd for C 8 H 1 6 0 3 C 59.97; H 10.07;

0 Found: C 60.28; H 9.93.

S trans-2-(l-Hydroxyethyl)-3-methyloxirane

To a stirred solution of 83.2 g of trans-3-penten-

2-ol in 1250 ml of methylene chloride at 00 a solution

of 200.1 g of 3-chloroperoxybenzoic acid in 750 ml of

methylene chloride was added dropwise during 2 hours

while the temperature of the reaction mixture was maintained at 0-10°. When addition was completed, the re- action mixture was allowed to warm to ambient temperature, and it was stirred for 18 hours. Excess peroxide was destroyed with an aqueous solution saturated with sodium sulfite. The reaction mixture was evaporated under reduced pressure while occasionally filtering out the precipitated

3-chlorobenzoic acid. The precipitate was washed with

hexane and the washings combined with the filtrate. The

combined liquid was evaporated under reduced pressure to a volume of 300 ml and poured into 600 ml of diethyl

e ether. The water layer was saturated with sodium chloride

and removed. The organic layer was washed with seven

.I portions of 50 ml each of an aqueous solution saturated

with sodium bicarbonate, then with two portions of

ml each of an aqueous solution saturated with sodium

chloride, and finally dried with sodium sulfate. The

mixture was filtered and the filtrate evaporated under

reduced pressure to a residual oil. The oil was distilled

under reduced pressure to give in two fractions 21.1 g of

trans-2-(l-hydroxyethyl)-3-methyloxirane; bp 78-81 0 C/40 mm.

•The base washes of the crude product described above were

combined and saturated with sodium chloride, then extracted

with four portions of 200 ml each of diethyl ether. The

combined extracts were dried with sodium sulfate and

filtered. The filtrate was evaporated under reduced pressure

to a residual oil. The oil was distilled under reduced

pressure to give 25.0 g of distillate; bp 77-78°/40 mm.

Y p LI

The two distillates were combined, giving 46.1 g of trans-

2-(l-hydroxyethyl)-3-methyloxirane.

Mixture of dl and meso-2,3,4-jentanetriols

A stirred solution of 172.3 g of trans-2-(1-hydroxy-

ethyl)-3-methyloxirane and 3.6 g of concentrated sulfuric

acid in 2239 ml of water and 100 ml of 1,4-dioxane was

heated at 550 during 18 hours. The reaction mixture was

cooled and neutralized with IN sodium hydroxide to the

phenophthalein end point, then evaporated under reduced

pressure until the salts present had crystallized out.

The viscous residue was taken up in methanol and filtered.

The filtrate was evaporated under reduced pressure to a re-

sidual oil. The oil was distilled under reduced pressure

to give in one fraction 184.6 g of a mixture of dl and

meso-2,3,4-pentanetriols; bp 110-112°/0.1-0.2 mm; nmr

spectrum was consistent with the assigned structure. trans-4-(erythro-l-Hydroxyethyl)-2,2,5- trimethyl-1,3-dioxolane and/or .cis-4- (threo-l-hydroxyethyl)-2,2,5-trimethyl- 1,3-dioxolane

This compound was prepared in the manner of Inter-

mediate A, using 184.6 g of a mixture of dl and meso-

2,3,4-pentanetriols, 104.2 g of acetone and 4.4 g of

p-toluenesulfonic acid in 1475 ml of dry hexane. The crude

reaction product was distilled under reduced pressure to

give in twenty-three fractions 102.8 g of what is believed

to be trans-4-(erythro-l-hydroxyethyl)-2,2,5-trimethyl-

1,3-dioxolane and/or cis-4-(threo-l--hydroxyethyl)-2,2,5-

trimethyl-l,3-dioxolanel bp 60-67'/4.5-5.0 mm.

Analyses calc'd for C 8 H 1 6 0 3 C 59.97; H 10.07;

Found: C 60.26, H 9.83.

dl-2,3,4-Pentanetriol

This compound was prepared in the manner of Inter-

mediate P, using 102.8 g of trans-4--(erythro--l-hydroxy- *0

000 ethyl)-2,2,5--trimethyl.-1,3-dioxolane and/or cis-4- S so o B S (threo-l-hydroxye' hyl)-2,2,5-trimethyl-l,3-dioxolane and seer, .1.0 5 339 ml of an aqueous 0.75% hydrochloric acid solution in 5 o go

*0 542 ml of absolute ethanol. The crude reaction product B See

0@ 5 was distilled under reduced pressure to give in one 9 5* S fraction 74.1 g of dl-2,3,4-pentanetriol; bp 106--ll0*/

0.02 mm.

5 S. r-2-Ethyl-c-5-hydrox t-6-dimethyl- Os.

em 1 ,3-dioxane s a.. C This compound was prepared in the manner of Inter- 55

*5 mediate A, using 74.1 g of dl- ,3,4-pentanetriol, 35.8 g

of propionaldehyde and 1.8 g of p-toluenesulfonic acid

in 589 ml of dry hexane. The crude reaction product was

purified by several distillations under reduced pressure,

and subsequent passes through a medium pressure liquid

chromatography unit with a silica gel column, eluted with

85:15 hexane:ethyl acetate. The appropriate combination of

fractions gave, when distilled under reduced pressure,

20.2 g of r-2-ethyl--c-5-hydroxy-c-4, t-6-dimethyl-l,3- dioxane; bp 78-83*/13-15 mm; ir and nmr spectra were

consistent with the assigned structure.

-h lk L I

Analyses calc'd for C H1603: C 59.987 H 10.07;

Found: C 60.27; H 10.35.

threo-2-Methyl-l,2,3-butanetriol

This compound was prepared in the manner of Inter-

mediate using 91.21 g of trans-2--methyl-2-buten-l-ol

(obtained by reduction of trans-2-methyl-2-butanal with

lithium aluminum hydride) and 2.55 g of tungstic oxide in

800 ml of water and 800 ml of 1,4-dioxane as solvent, and

43.23 g of hydrogen peroxide (144.10 g of an aqueous

solution 30% in hydrogen peroxide). The crude reaction

f.. product was distilled under reduced pressure using a short ft ft ft f ft t f path distilling system to give in one fraction 82.02 g rS of threo-2-methyl-l,2,3-b-itanetriol; bp 110 0 /less than ft.

0.001 mm.

T. r-2-Ethyl-c-5-hydroxy-t-4, 1,3-dioxane ft This compound was prepared in the manner of Inter- ft t. mediate A using 50.00 g of threo-2-methyl-l,2,3-butane-

triol, 24.15 g of propionaldehyde, and 1.18 g of p-toluene- ft ft fto sulfonic acid in 250 ml of dry hexane. The crude reaction .ffftC ft I product was distilled under reduced pressure to give in ten

fractions 30.02 g of r-2-ethyl-c-5-hydroxy-t-4,

dimethyl-1,3-dioxane; bp 410/0.96 mm; ir and nmr spectra

were consistent with the assigned structure.

Analyses calc'd for C 5H2203: C 71.97; H 8.86;

Found: C 72.22; H 8.91.

The compounds of the invention were prepared by

causing a substituted 5-hydroxy-1,3-dioxai. in a solvent

(toluene, for example) to react with an alkali metal base

at temperatures from ambient to that of solvent reflux to

obtain the alkali metal alcoholate, which was etherified

by reaction at solvent reflux temperature with an aryl-

methyl halide (for example an arylmethyl chloride or

bromide) or with a heteroarylmethyl halide (such as

2-chloromethylfuran). Preferred alkali metal bases were

t 10 sodium compounds. In an optional process, especially

useful to obtain a compound in which the 2-substituent was

C vulnerable to attack during treatment (for example,

chloromethyl) with the alkali metal base, or was so bulky o g Lb as to impede selective distillation of the

1,3-dioxane (phenyl, for example), a compound of the

invention containing appropriate 4- and 5-substituents was

be subjected to acid hydrolysis, yielding a 1,3-diol, which

was caused to react in presence of an acid catalyst 2' (p-toluenesulfonic acid, for example) with an appropriate

carbonyl compound (benzaldehyde, for example) or its

acetal (chloroacetaldehyde diethyl acetal, for example) in b a solvent (hexane, for example) at reflux, yielding a 0~

1,3-dioxane which carried the desired 2-substituent and

has retained the 4- and 5-substituents with the desired

configuration.

Example I

r-2-Ethyl-c-5-(2-fluorobenzyloxy)- -4-methyl-l,3-dioxane

A 2.53-gram portion of a suspension of sodium hydride

in mineral oil (1:1 by weight) was placed in a reaction

vessel and washed witn two 50-ml portions of dry hexane and

two 50-ml portions of dry toluene. One hundred ml of dry

toluene was added to the sodium hydride and stirred while

7.00 g of r-2-ethyl-c-5-hydroxy-c-4-methyl-l,3-dioxane was

added dropwise, which required 15 minutes, during which the

exothermic reaction raised the temperature of the reaction

mixture from 230 to 33°. The reaction mixture was heated

under reflux for 5.5 hours, and cooled to ambient tempera-

ture, at which 7.62 g of 2-fluorobenzyl chloride was added

during 5 minutes. The reaction mixture was heated under

reflux for 18 hours. The reaction mixture was washed with

three 50-ml portions of cold water (until washwater showed

approximately pH The organic layer was separated,

dried with sodium sulfate, and filtered. The filtrate was 6e6

concentrated under reduced pressure to a residual 11.87 g of yellow liquid, which was distilled under reduced pres-

sure, yielding 7.85 g of r-2-ethyl-c-5-(2-fluorobenzyloxy)- c-4-methyl-l,3-dioxane; bp 95.5-980/0.05-0.075 mm; ir and

nmr spectra were consistent with the assigned structure.

Analyses calc'd for C14H29FO3: C 66.12; H 7.53;

Found: C 66.40; H 7.55.

J I I I I

Example II

r-2-Ethyl-c-4-methyl-c-5-(2-methylbenzyloxy)-l,3-dioxane

The procedure of Example I was followed, using 2.53 g

of the sodium hydride-mineral oil suspension and 7.00 g of

r-2-ethyl-c-5-hydroxy-c-4-methyl-l,3-dioxane, and 7.41 g of

2-methylbenzyl chloride instead of 2-fluorobenzyl chloride.

The washed, dried, and filtered reaction mixture was con-

centrated under reduced pressure to a residual 11.78 g of

dark yellow liquid. This was purified by column chromato-

graphy, using a silica gel column eluted with high-boiling

petroleum ether, and high-boiling petroleum ether:ethyl

acetate (98:2) until 245 fractions were collected. Cuts

95-122 were combined and concentrated to yield 6.32 g of

S yellow liquid. The two portions were distilled under reduced pressure and the combined distillates comprised

6.90 g of r-2-ethyl-ic-4-methyl-c-5-(2-methylbenzyloxy)-

1,3-dioxane; bp 10l-1060/0.05-0. 075 mm; ir and ir spectra

were consistent with the assigned structure.

Analyses calc'd for C15H2203: C 71.97; H 8.86;

Found: C 72.02; H 8.89.

Example III

c-5-(2-Chlorobenzyloxy)-r-2-ethyl-c-4-methyl-l,3-dioxane

The procedure of Example I was followed, using 2.53 g

of the sodium hydride-mineral oil suspension and 7.00 g of

r-2-ethyl-c-5-hydroxy-c-4-methyl-l,3-dioxane, and 8.48 g

of 2-chlorobenzyl chloride instead of 2-fluorobenzyl

chloride. The washed, dried, and filtered reaction mixture was concentrated under reduce3 pressure to a resid- ual 12.96 g which was distilled under reduced pressure, yielding 7.46 g of c-5-(2-chlorobenzyloxy)-r-2-ethyl-c-4- methyl-1,3-dioxane; bp 110-114°/0.32-0.40 mm; ir and nmr spectra were consistent with the assianed structure.

Analyses calc'd for C 1 4 H 1 6 C103: C 62.10; H 7.07;

Found: C 62.40; H 7.09.

Example IV

c-5-Benzyloxy-r-2-ethyl-c-4-methyl-l,3-dioxane

The procedure of Example I was followed, using 2.52 g

of the sodium hydride-mineral oil suspension and 7.0 g of 0*S*

r-2-ethyl-c-5-hydroxy-c-4-methyl-1,3-dioxane, and 6.62 g of

*benzyl chloride instead of 2-fluorobenzyl chloride. After

being heated at reflux 16 hours, the reaction mixture was S* washed with five 100-ml portions of water (until washwater

showed approximately pH The organic layer was

separated, dried with sodium sulfate, and filtered. The

filtrate was concentrated under reduced pressure to a

residual 11.56 g, which was distilled under reduced pres- "0 sure, yielding 6.57 g of c-5-benzyloxy-r-2-ethyl-c-4-

methyl-1,3-dioxane; bp 110-1140/0.01 mm; ir and nmr spectra

were consistent with the assigned structure. *0*asS

Analyses calc'd for C4H 2003: C 71.15; H 8.53;

Found: C 71.43; H 8.33.

Following the general procedures of Examples I-IV,

these further compounds were prepared:

-26-

-i,

Example

c-5-Benzyloxy-rE-2-isopropyl-c-4-methyl-1 ,3-

dioxarne; bp 110-113*/0,,020 mm;- C 72.20%, H 8.57%.

VI c-5- (2-FlooezPl-I Icn A-t I- 1,3-dioxane; bp 103-105'/0.020 mm; C 67.14%,

VI soprop-c4mehy--5(-mtylc-4-m xy)

%0 VI 2Clrbnyo )-r--ispoy-c- ethyl-

1,3-dioxane; bp 126-130o/0.020 mm; C 62.96%,

H 7.25%. IX c-5--Eenzyoxy--2-ethyl-c-4-propyl-1,3-dioxane;

bp 1250/0.01 mm; C 72.38%, H 9.29%. 0 a Xr-2-Ethyl-c-5--(2-fluorobenzyloxy)-c-4-propyl-

1,3-dioxane; bp 1400/0.01 mm; C 68.20%,

S H 8.54%. Xi r-2-Ethyl--c-5-(2-methylbenzyloxy)-c-4-propyl-

S....1,3-dioxane; bp 1300/0.010 mm; C 73.10%, H 9.41%. XII c-5-(2-Chlorobenzyloxy)-r-2-ethyl-c-4-propyl-

1,3-dioxane; bp 120-125'/0.01 mm; C 64.00%, 00 H 7.57%.

Comparative Example XIII

r-2-Ethyl-c-4--methyl-t-5- (2-methylbenzyloxy ,3-dioxanle

This compound was prepared in the manner of Example I,

using 2.48 g of r-2-ethyl-t-5-hydroxy-c-4-methyl-1,3-

-27-I

I re.

dioxane (Intermediate 2.60 g of 2-methylbenzyl

chloride, and 0.45 g (0.90 g of a 50% dispersion in

mineral oil) of sodium hydride in 70 ml of toluene. The

crude reaction mixture was distilled to give 2.41 g of

r-2-ethyl-c-4-methyl-t-5-(2-methylbenzyloxy)-l,3-dioxane;

bp 93-950/0.011 mm, n25=1.5284. The nmr and the ir spectra

were consistent with the assigned structure.

Analyses calc'd for C 1 5 H 2 203: C 71.97; H 8.86;

Found: C 72.60; H 8.90.

*10 Example XIV

r-2-Ethyl-t-4, t-5, c-6-trimethyl-c-5-(2-methylbenzyloxy)-

1,3-dioxane in mixture with what is believed to be 2-ethyl-

4,5-dimethyl-4-[1-(2-methylbenzyloxy)ethyl]-1,3-dioxolane. e A stirred solution of 6.22 q of the mixture of r-2-

ethyl-c-5-hydroxy-t-4, t-5, c-6-trimethyl-l,3-dioxane and

what is believed to be 2-ethyl-4,5-dimethyl-4-(l-hydroxy-

ethyl)-1,3-dioxolane (Intermediate J) and 2.42 g of sodium

ethoxide (an ethanolic solution 15% in sodium ethoxide) in dry toluene was heated to a temperature which caused the

26 ethanol to be removed azeotropically from the reaction mix-

ture. Additional toluene was added to the reaction mixture

as needed. When the temperature of the distillate reached

*"1100, 50 ml of the distillate was collected; and the

reaction mixture cooled to ambient temperature. To the

reaction mixture was added, in one portion, a solution of

5.02 g of 2-methylbenzyl chloride. The reaction mixture

was heated under reflux for 20 hours, then poured into u rr ml cold water. The toluene layer was separated and the water layer washed with three portions of 50 ml each of toluene. The combined toluene layers were washed with three portions of 25 ml each of water, then dried with sodium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure to a residue.

The residue was distilled under reduced pressure using

a short-path distilling system. One fraction of 3.09 g of

distillate, bp 25-420/0.01 mm was obtained. Gas chromato-

graphic analysis of this fraction indicated a mixture con-

Staining a large portion of starting o-methylbenzyl chloride.

S4 The distillation vessel residue from this distillation, weight 5.59 g, was distilled under reduced pressure to give

in one fraction 4.58 g of clear liquid distillate, bp

118-122°/0.07 mm. Gas chromatographic analysis of the

distillate indicated it to be a mixture of 62% r-2-ethyl-

t-4, t-5, c-6-trimethyl-c-5-(2-methylbenzyloxy)-l,3-dioxane

and 23% of what is believed to be 2-ethyl-4,5-dimethyl-4-

[l-(2-methylbenzyloxy)ethyl]-l,3-dioxolane. The nmr

spectrum was consistent with the assigned structures.

Comparative Example XV

2* r-2-Ethyl-c-4,t-4,t-5-trimethyl-c-5-(2-methylbenzyloxy)- 1,3-dioxane.

This compound was prepared in the manner of Example I,

using 5.78 g of r-2-ethyl-c-5-hydroxy-c-4,t-4,t-5-

trimethyl-l,3-dioxane (Intermediate K) 5.13 g of 2-methyl-

benzyl chloride, 0.88 g (1.75 g of a 50% dispersion with

II I _I r

mineral oil) of sodium hydride in 100 ml of dry toluene.

The crude reaction product was subjected to column

chromatography using 150 g of silica gel in a 3.6 cm

glass column. Elution was accomplished with 100%

high-boiling petroleum ether, 99:1 high-boiling petroleum

ether/ethyl acetate, 95:5 high-boiling petroleum ether/

ethyl acetate, and 100% ethyl acetate. Fractions 70-156

were combined to lield 4.19 g of residual oil, after

evaporation of the solvents. The residual oil was distilled using a short-path distilling system to give, in

two fractions, 1.06 g of r-2-ethyl-c-4,t-4,t-5-trimethyl-

e c-5-(2-methylbenzyloxy)-l,3-dioxane; bp 89.5-930/0.005 mm.

The ir and the nmr spectra were consistent with the assigned

structure.

Analyses calc'd for C 1 7 H2603: C 73.34; H 9.41;

Found: C 73.38; H 9.56

Example XVI

c-5-Benzyloxy-c-4-methyl-r-2-propyl-l,3-dioxane

A stirred mixture of 6.00 g of c-5-hydroxy-c-4-methyl-

r-2-propyl-l,3-dioxane (Intermediate F) and 3.40 g of sodium

methylate (13.60 g of a methanolic solution 25% in sodium

methylate) in 150 ml of dry toluene was heated to a tempera-

S* ture at which the methanol was removed by forming an azeo-

trope with toluene. After the methanol had been removed,

dry toluene was added to replace the volume of azeotrope

lost, the mixture was cooled to approximately 800 and 7.90 g

of benzyl chloride was added dropwise. When the addition had been completed, the reaction mixture was heated under reflux for 19 hours. After it had been cooled to room temperature, the mixture was washed with six 60-mi portions of water, once with a 60-mi portion of salt solution, and dried over anhydrous sodium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure to a residual 14.6 g, which was distilled under reduced pressure, yielding 8.0 g of c-5-benzyloxy-c-4-methyl-r-

2-propyl-l,3-dioxane; bp l07-l09*/0.0l3 mm; ir and nmr

spe~ctra were consistent with the assigned structure.

U. Analyses calc'd for C 15H 2203: C 71.97; H 8.86; U U

*5 Found: C 72.20; H 9.12. U 4

U. Following the procedure of Example XVI or procedures U.

earlier exemplified, these further compounds were prepared: 4

a eq U Example

XVII c-5-(2-Fluorobenzyloxy)-c-4-miethyl-r-2-propyl-

1,3-dioxane; bp 143-1450/0.015 mm; C 67.09%, a.. H 8.02%. a U..

XVIII c-4-Me-thyl-c-5-(2-methylbenzyloxy)-r-2-propyl- a.

1,3-dioxane; bp 114-1181/0.005 mm; C 72.35%,

H 9.09%.

XIX c-5- (2-Chlorobenzyloxy )-c-4-methyl-r-2-propyl- V U 1,3-dioxane; bp 114-1181/0.005 mm; C 63.36%,

H 7.31%.

XX c-5-Benzyloxy-rE-2, c-4-diethyl-l, 3-dioxane;

bp 113-1150/0.15 mm; C 72.25%, H 8.74%.

XXI- r-2,c-4--Diethyl-c-5-(2--fluorobenzyloxy)-

1,3-dioxane; bp 115-117*/0.15 mm; C 67.39%,

H 7.71%.

xxii r-2,c-4--Diethyl-c-5-(2-methylbenzyloxy)-

1,3-dioxane; bp 118-120*/0.10 mm; C 73.01%,

H 8.98%.

XXIII c-5-(2-Chiorobenzyloxy)-r-2,c-4-diethyl-

1,3-dioxane; bp 127-1301/0.15 mm; C 63.57%,

H 7.30%.

XXIV- c-5-Benzyloxy-cS-4-ethyl-r-2-methyl-1,3-dioxane; bp 118-1230/0.015 mm; C 71.10%, H 8.60%.

1,3-dioxane; bp 115-1180/0.11 mm; C 66.41%,

H 7.61%.

XXVI c-4-Ethyl-r-2-methyl-c-5-.(2-methylbenzyloxy)- 1,3-dioxane; bp 114-120o/0.06 mm; C 72.25%,

H 8.84%.

XXVII- c-5-(2-Chlorobenzyloxy)-c-4-ethyl-r-2-methyl- 1,3-dioxane; bp 123-128*/0.013 mm; C 62.39%, 2 H 6.96%.

XXVIII -c-5-Benzyloxy-cS-4-ethyl-r-2-isopropyl-1,3-

dioxane; bp 106-108'/0.01 mm; C 73.02%,

H 9.46%.

XXIX- c-4-Ethyl-c-5-(2-fluorobenzyloxy)-r-2-isopropyl-

1,3-dioxane; bp 115-118*/0.01 mm; C 68.36%,

H 8.26%.

xxx c-4-Ethyl-r-2-isopropyl-c-5-(2-methylbenizyloxy)-

1,3-dioxane; bp 105-106*/0.03 mm; C 73.65%,

H 9.58%.

XXXI- c-5-(2-Chlorobenzyloxy)-c-4-ethyl-r-2-isopropyl-

1,3-dioxane; bp 123-125'/0.01 mm; C 64.51%,

H 7.93%.

The procedure used for Intermediate A was used employ-

ing threo-2-(2-methylbenzyloxy)-1.,3-butanediol (Intermediate

P) and threo-2-benzyloxy-1,3-butanediol, with an appropriate

10 carbonyl compound or its acetal to prepare: *.V

Example S

XXXII c-4-Methyl-c-5- (2-methyibenzyloxy)-r-2-phenyl- 5 5 4

1,3-dioxane; bp 1650/0.005 mm; mp 52-57'; SW.

C 76.12~,- H 7.60%.

XXXIII- cis-2-Methyl-3-I,2-methylbenzyloxy)

bp 135-137*/0.012 mm;

C 74.15%, H 9.20%.

XXXIV-A- r-2-Chloromethyl-c-4--methyl-c--5-(2-methyl- *04

benzyloxy)-1,3-dioxane; bp 120-121'/0.005 mm; S

C 62.41%, H 7.20%. 2o XXXIV-B- r-2--Chloromethyl-t--4-methyl-t-5- (2-methyl- 4 *5 5* benzyloxy)-1,3-dioxane; bp unrecordable; nmr 4

S spectrum was consistent with the assigned

structure.

XXXV c-5-Benzyloxy-rE-2-chloromethyl-c-4-methyl-

1,3-dioxane; bp 102-110'/0.012 mm; C 60.72%,

H 6.40%.

I 1

Example XXXVI

cis-4-Methyl-5-(2-methylbenzyloxy)-1,3-dioxane

Th.s compound was prepared in the manner of Inter-

mediate A using 12.00 g of threo-2-(2-methylbenzyloxy)-

1,3-butanediol (Intermediate 3.33 g of paraformaldehyde,

and 0.30 g of p-toluenesulfonic acid in 300 ml of dry

hexane. The crude reaction product was recrystallized from

ethanol/water to give 7.40 g of cis-4-methyl-5-(2-methyl-

benzyloxy)-1,3-dioxane; mp 540; nmr spectrum was consistent

with the assigned structure.

Analyses calc'd for C 1 3 H 1 8 03: C 70.24; H 8.16; Found: C 70.46; H 8.07.

Comparative Example XXXVII

5-Methyl-5-(2-methylbenzyloxy)-1,3-dioxane

This compound was prepared in the manner of Inter-

mediate A using 6.00 g of 2-methyl-2-(2-methylbenzyloxy)-

1,3-propanediol (Intermediate 1.66 g of paraformaldehyde,

and 0.13 g of p-toluenesulfonic acid in 150 ml of dry hexane. *9*

The crude reaction product was distilled under reduced pres-

sure using a short path distilling system to give in one

fraction 3.64 g of 5-methyl-5-(2-methylbenzyloxy)-1,3- dioxane; bp 0l6-1080/0.01 mm; ir and nmr spectra were con-

S* sistent with the assigned structure.

Analyses calc'd for C13H1803: C 70.24; H 8.16;

Found: C 70.02; H 8.31.

The procedures exemplified previously were used to

prepare the following 4-substituted-l,3-dioxanes:

Example,

XXXVIII c-5-Benzyloxy-rE-2-ethyl-c-4, c-6-dimethyl-.

1,3-dioxane; bp 108-1101/0.011 mm, which

solidified; mp 31-33O; C 72.30%, H 8.92%.

XXXIX c-5-Benzyloxy-r-2-ethyl-c-4,t-6-dimethyl-

1,3-dioxane; bp 92-94'/0.05 mm; C 72.10%,

H 9.15%.

XL c-5-Benzyloxy-r-2-ethyl-t-4,

1,3-dioxane; bp 109-110o/0.011 mm; C 72.~22%,

H 8.91%.

XLI r-2-(2-Cyanoethy1)-c-4-methy-c-5--(2-methyl-

benzyloxy)-1,3-dioxane; mp 50-51.51; C 70.04%, H .5% *0

XLII r-2-Ethyl-c-5--[ (2-furyl)methoxy]-c-4-methyl- 001,3-dioxane; bp '70-72*/0.003 mm; C 64.02%,

H 7.99%.

XLIII -cis-5-Benzyloxy-4-ethyl-1,3-dioxane; bp 96-100'/ go

*0 0.01 mm; C 70.52%, H 8.20%,

XLIV c-5-Benzyloxy-rE-2-ethyl-c-4-isopropyl-1,3-

aioxane; bp 108-125*/0.01 mm; C 72.11%, H 9.02%.

XLV r-2-Ethyl-c-5-(2-fluorobenzyloxy)-c-4-isopropyl-

o 1,3-dioxane; bp 100-110*/0.005-0.027 mm;

0 C 68.103, H 8.41%.

XLVI -r-2-Ethyl-c-4-isopropyl-c-5-(2-fluorobenzyloxy)-

1,3-dioxane; bp 12:--124'/0.11-0.12 mm; C 73.49%,

H 9.47%.

MOWN

XLVII c-5-(2-Chlorobenzyloxy)-r-2-ethyl-c-4-isopropyl-

1,3-dioxane; bp 116-117*/0.022 mm; C 65.13%,

H 7.91%.

XLVIII- c-5-Benzyloxy-r-2,c-4-dimethyl-1,3-dioxaie; bp

90-94*/O.0O8 mm; C 70.03%, H 8.18%.

XLIX c-5-(2-Fluorobenzyloxy)-r-2,c-4-dimethyl-1,3-

dioxane; bp 83-83.5'/0.009 mm; C 64.81%, H 7.42%.

L -r-2,c-4-Dimethyl-c-5-(2-methylbenzyloxy)-1,3-

dioxane; bp 100-105*/0.005 mm; C 71.16%, H 8.64%.

:410 LI c-5-(2-Chlorobenzyloxy)-r-2,c-4-dimethyl-1,3-

dioxane; bp 1130/0.023 mm; C 60.51%, H 6.76%.

LII c-5-Benzyloxy-rE-2-tert-butyl-c-4-methyl-1,3- dioxane; bp 84-870/0.006 mm; C 72.96%, H 9.41%. LIII r-2-tert-Butyl-c-5-(2-fluorobenzyloxy)-c-4-

methyl-1,3-dioxane; bp 79-81'/0.008 mm; C 67.84%,

H 8.37%.

LIV r-2-tert-Butyl-c-5-(2-methylbenzyloxy)-c-4- a. methyl-1,3-dioxane; bp 95-99*/0.13 mm; C 72.96%,

H 9.52%. ~20LV r-2-tert-Butyl-c-5-(2-chlorobenzyloxy)-c.-4-

methyl-1,3-dioxane; bp 107-112o/0.014 mm; C 63.99%,

H 7.77%.

aSLVI r2-Ethyl-c-5-(3-fluorobenzyloxy)-c-4-methyl-1,3- r

dioxane; bp 101.5-102*/0.015-0.02 mm; C 66.38%,

H 7.66%.

LVII r-2-Ethyl-c-5-(4-fluorobenzyloxy)-c-4-methyl--1,3-

dioxane; bp 92.5-93*/0.01 mm; C 65.81%, H 7.71%.

w T;

LVIII c-5-(2,6-Difluorobenzyloxy)-r-2-ethyl-c-4-methyl-

1,3-dioxaie; bp 82-84o/0.004 mm; C 61.90%,

H 6.87%.

LIX- r-2-Ethyl-c-4-methyl-c-5-(3-methylbenzyloxy)-

1,3-dioxane; bp 88-90.50/0.035 mm; C 71.79%,

H 9.03%.

LX r-2-Ethyl-c-4-methyl-c-5-(4-methylbenzyloxy)-

1,3-dioxane; bp 106-1101/0.006 mm; C 71.71%,

H 8.85%.

0.0LXI r-2-Ethyl-c-4-methyl-c-5-(2,6-dimethylbenzyloxy)-

1,3-dioxane; mp 74-74.5O; C 72.76%, H 8.90%.

:LXII c-5-(3-Chlorobenzyloxy)-r-2-ethyl-c-4-methyl- 1,3-dioxane; bp 146.5-147.5'/0.29 mm; C 62.12%, IH 6.96%.

*LXIII c-5-(4-Chlorobenzyloxy)-r-2-ethyl-C-4-methyl-

1,3-dioxane; bp 109.5-111.5'/0.03 mm; C 61.89%,

H 7.04%.

LXIV c-5-(2,6-Dichlorobenzyloxy)-r2-ethy-c-4-iaethy1-

**1,3-dioxane; bp 131-132'/P.02 mm; C 55.21%, H 5.94%.

LXV -4-Butyl-r-2-ethyl-c-5-(2-fluorobenzyloxy)-1,3-

dioxane; bp 136-137*/0.15 mm; C 69.14%, H 8.34%.

LXVI c-4-Butyl--r-2-ethyl-c-5-(2-methylbenzyloxy)-1,3-

dioxane; bp 119-122*/0.013-0.019 mm; C 74.39%,

H 9.68%.

LXVII c-4-Butyl-c-5-(2-chlorobenzyloxy)-r-2-ethyl-1,3-

dioxane; bp 154-159*/0.25 mm; C 65.48%, H 8.01%.

LXVIII -r-2-Ethyl-c-5- (2-fluorobenzyloxy)-c-4-pentyl-1,3-

dioxane; bp 11.9--121'/0.019 mm; C 69.61%, H 8.57%.

LXIX r-2-Ethyl--c-5-(2-methylbenzyloxy)-c-4-pentyl-1,3- kJF 1, JJ U. /A AnJ~ A IIL I- I*.7JA

H 9.88%.

LXX c-5-(2-Chlcw~obenzyloxy)-r-2-ethyl-c-4-pentyl-1,3-

dioxane; bp 136-137.51/0.02 mm; C 66.48%,

H 8.48%.

LXXI c-5-Ben~zyloxy-c-4-ethyl-r-2-propyl-1,3-dioxane;

bp 105-1101/0.02 mm; C 72.70%, H 9.29%.

A 0 LXXII c-4-Ethyl--c-5-(2-methylbenzyloxy)-r-2-propyl- A.

.1,3-dioxane; bp 110-116*/0.02 mm; C 73.13%, 0 0 A A 00

A. H 9.39%. C 000 LXXIII -c-5-Benzyloxy-r-2-butyi-c-4--methyl-1,3-dioxane;

.A 0

S. bp 95-102*/0.003 mm; C 72.61%, H 8.91%.

LXXIV r-2-Butyl-c-5- (2-fluorobenzyloxy)-c-4-methyl-

A. 1,3-dioxane; bp 101-107*/0.005 mm; C 68.06%, A..

H 8.00%. A AS LXXV r-2-Butyl-c-4--methyl-c-5-(2-methylbenzyloxy)-1,3- .20 dioxane; bp 1150/0.005 mm; C 73.37%, H 9.52%.

LXXVI r-2-Butyl-c-5-(2-chlorobenzyloxy)-c-4-methyl- 5O *5 1,3-dioxane; bp 93-1060/0.003 mm; C 64.63%, 0 H 7.62%. 1

LXXVII -r-2-Hexyl-c-4-methyl-c-5-(2-methylbenzyloxy)-

1,3-dioxaie; bp 140-150*/0.015 mm; C 74.38%,

H 9.93%.

U-

LXXVIII -r-2-Methoxymethyl-c-4-methyl--c-5-(2-methyl-

benzyloxy)-1,3-dioxane; bp 124-128*/0.04 nmn;

C 67.48%. H 8.56%.

LXXIX- r-2-Bromomethyl-.c-4-methyl-cr5-(2--methyl-

benzyloxy)-1,3-dioxane; bp 132.5-135*/0.016 ynm;

C 53.46%, H 6.06%.

LXXX r-2-Ethyl-c-5-(2-fluorobenzyloxy)-c-4,c-6-

dimethyl-1,3-dioxane; bp 101-1030/0.03 mm; mp 43-.45.50; C 67.10%, H 7.76%.

LXXXI r-2-'Ethyl-c-4,c-6-dimethyl-c-5-(2-methyl-

:~:benzyloxy)-1,3-dioxane; bp 1120/0.04 mm; mp

56-58*; C 72.62%, H 9.00%. LXXXII -c-5-(2-Chlorobenzy1oxy)-r-2-ethyl-O-4,c-6

see dimethyl-1,3-dioxane; bp 112-1180/0.013 mm;

0 mp 58.5-600; C 63.28%, H 7.42%.

LXXXIII -r-2-Ethyl-c-5-(2-fluorobeloxy)-c-4,t-6

dimethyl-1,3-dioxane; bp 102-1060/0.025 mm;

C 67.40%, H 8.04%.

LXXXIV -r-2-Ethyl-c-4,t-6-dimethyl-c-5-(2-methylN

benzyloxy)-1,3-dioxane; bp 98-1000/0.015-

0.020 mm; C 72.73%, H 8.86%. 6g LXXXV c-5-(2-Chlorobenzyloxy)--r-2-ethyl-c-4,t-6-

6 dimethyl-1,3-dioxane; bp 106-1080/0.01 mm;

C 63.37%, H 7.54%.

LXXXVI -r-2-Ethyl-c-5-(2-fluorobeflzyloxy-t4,t-5

dimethyl-1,3-dioxane; bp 118-1220/0.015 nin;

C 67.42%, H 8.16%.

LXXXVII -c-5-(2--Chlorobenzyloxy)--r-2-ethyl-t-4,t-5-

dimethyl-1,3--dioxane; bp 1100/0.01 mm;

C 63.25%, H 7.38%.

LXXXAVII.I-. r-'Z-C-yanomieth'y1,-c-4-methy1-c-5-- (2-methyl-

benzyloxy)-1,3-dioxane; bp 167-177*/0.008 mm;

C 69.23%, H 7.39%.

LXXXIX r-2--Ethyl-c-4-methyl-c-5- [(2-pyridyl )methoxy]

1,3-dioxcane; bp 85-870/0.004 mm; C 65.98%,

H. 7.96%. XC r-2-Ethyl-c-4-methyl-c-5-[(3-pyridylymethoxy]-

1,3-dioxane; bp 96-98'/0.003 mm; C 66.00%, H 8.11%.

*0XCI r-2-Ethyl-c-4--methyl-c-5-[(4-pyridyl)methoxy]-

1,3-dioxaie; bp l10-112*/0.005 mm; C 66.07%,

o~ H 8.32%. XCII r-2 -Ethyl-c-4-methyl--c-5-[(2-thienyl)methoxy]-

CC. 1,3-dioxane; bp 98-100'/0.005 mm; C 59.53%, H 7.33%. XCIII- cis-4-Ethyl-5-(2-fluorobenzyloxy)-1,3-dioxane;

mp 72.5-731; C 65.02%, H 6.90%. XCIV cis-4-Ethyl-5-(2-methylbenzyloxy)-i.,3-dioxane;

0* mp 71.5-730; C 70.88%, H 8.27%. XCV- cis-4-Ethyl-5--(2-chlorobenzyloxy)-1,3-dioxane;

mp 73-75O; C 60.62%, H 6.59%.

XCVI &is-4-Fthy1-5-(2,6-difluorobenzyloxy)-1,3-

dioxane; mp 91-92o; C 60.58%, H.6.46%.

XCVII cis-5-Benzyloxy-4-methy'L-1,3-dioxane; mp 35-361;

C69.34%, H 7.78%.

XCVIII -cis-5-(2-Fluorobenzyloxy)-4-methyl-1,3-dioxane;

mp 38-40*; C 64.03%, H 6.86%.

XCIX cis-5-(2-Chlorobenzyloxy)-4--methyl-l,3-dioxane;

mp 73-75'; C 59.31%, H 6.29%.

C -cis-5-(2,6-Difluorobenzyloxy)--4-methyl-l,3-dioxane;

mp 64-661; C 58.81%, H 5.93%.

CI c-5-Benzyloxy-c-4-tert-butyl-r-2-ethyl-1, 3-

dioxane; bp 100-1050/0.007 mm; C 73.19%, H 9.23%.

CII c-4-tert-Buityl-r-2-ethyl-c-5-(2-fluorobenzy'Loxy)-

:-.101,3-dioxane; bp 101-1030/0.02 mm; C 68.96%,

H 8.71%.

The herbicidal activities of the compounds of this invention were demonstrated as follows: Rows

of seeds of lima beans (Phaseolus lunatus), corn (Zea

*may), wild oats (Avena fatua), lettuce (Lactuca

sativa), mustard (Brassica juncea) and crabgrass

(Digitaria sanguinalis) were planted in shallow flat-bed

trays (20 cm x 15 cm x 8 cm) containing approximately

5 cm of sandy loam soil, and a thin layer of soil (approximately 1 cm) was applied to the surface to

4 cover the seeds. Pots containing viable tubers of

purple nutsedge Cyperus rotundus) planted at a depth

of 2,5 cm were used.

For preemergence tests, an aqueous acetone solution

of the test compound (using sufficient acetone to

obtain solution) was sprayed on the soil covering

the seeds in the .trays (or the tubers in the pots)

at a rate equivalent to 8.96 kilograms/hectare or submultiples thereof (4.48, 2.24, 1.12, 0.56, 0.28 kg/ha), using a total volume equivalent to 760 liters/- hectare. The trays and pots were maintained under intermittent high-intensity light conditions in the greenhouse for 10 to 14 days, after which the herbicidal efficacy of the compound was assessed. Individual plant species were examined in comparison with untreated plants.

Tables 1 and 2 list results collected in preemergence

tests with compounds of the present invention, shown

together with results obtained in parallel tests of com-

pounds disclosed in the prior art (which bear only hydrogen

on the carbons in the 4-position and the 6-position of the

1,3-dioxane).

In Table 1 it is seen that compounds of Examples I,

II, III, and IV are herbicidally active against grassy

species such as corn and crabgrass at rates of appli-

cation of 0.56 kg/ha or below, while the standard for

comparison, a prior art 1,3-dioxane with only hydrogen

in the 4- and 6-positions is clearly less active. The compounds of Examples I, II, and III are also approxi-

mately twice as effective against purple nutsedge at rates

of 2.24 kg/ha as the prior art comparison compound.

The compound of Comparative Example XV is seen to be

altogether inactive at 4.48 kg/ha or below, and shows

only a trace of activity against corn and crabgrass at

8.96 kg/ha. This compound differs from the prior art com-

parison compound in having two methyl groups in the 4-

position of the dioxane ring, and is essentially without

-42-

I

~I

herbicidal activity. The compound of Comparative Example

XIII is seen to be totally inactive at 8.96 kg/ha. This

compound differs from the compound of Example II only in

the stereochemical relationship between the 2-ethyl sub-

stituent and the 5-(2-methylbenzyloxy) substituent. In

the active compound of Example II there is a cis relation-

ship between these substituents, and in the inactive com-

pound of Comparative Example XIII, there is a trans

relationship between these substituents.

10 Other varieties of plant species were used for further

preemergence evaluations. These included coffeeweed

(Sesbania spp.), sugarbeet (Beta vulgaris), soybeans 0

(Glycine max), cotton (Gossypium hirsutum), sorghum

°(Sorghum vulgare), sicklepod (Cassia obtusifolia), barley

(Hordeum vulgare), barnyardgrass (Echinochloa .crusgalli),

peanut (Arachis hypogaea), safflower (Carthamus

tinctorious), tomato (Lycopersicon esculentum), rice

'(Oryza sativa), wheat (Triticum aestivum), morning glory C (Ipomoea purpurea), rape (Brassica campestris), prickly S.

sida (Sida spinosa giant foxtail (Setaria faberii),

oats (Avena sativa), downy brome (Bromus tectorum), and

sesbania (Sesbania exaltata).

An extended evaluation of compounds of the inven-

tion compared the compound of Example I with Comparison

Standard A, the compound of Example II with Comparison

Standard B, and the compound of Example III with Com-

parison Standard C. The Comparison Standards are within

the scope of prior art disclosures and A, B, and C each

I I

differs from the compound with which it is being compared

only in having no 4-substituent. Inspection of Table 2, in

which results of these comparisons are recorded, shows the

4-substituted dioxanes of the present invention to be more

activeh than teir prior art counterparts withoLut 4-sub-

stitution. In addition the prior art dioxane (Comparison

Standard D) with a 5-methyl substituent instead of the 4-

methyl substituent of the compounds of the present invention

was again found less herbicidally active against corn, wild

oats, crabgrass, barnyardgrass, giant foxtail, oats, barley,

and rice than the compounds of the present invention. The 0See o, compounds of the present invention were less toxic to wheat

0e than the prior art dioxane, and were non-toxic to lettuce,

tomato, peanut, and essentially non-toxic to soybeans, 0. 0 cotton, and sugarbeet, at rates of 4.48 kg/ha or less.

Results of preemergence tests with additional com-

pounds of the invention are recorded in Table 3. Com-

parison of the results with the compounds of Example XXXVI

and Comparative Example XXXVII is of interest. Neither *6

*2o compound contains a 2-substituent other than hydrogen, and

the compound of Example XXXVI (with a cis-4-methyl sub-

stituent) is strongly active against the three grasses,

while the compound of Comparative Example XXXVII (with

a 5-methyl substituent) is definitely less active at 8.96

kg/ha.

For postemergence tests, the trays in which seeds had

been planted were maintained in the greenhouse until the

first trifoliate leaves of the bean plants were unfolding.

_L ~Y

The test plants were then sprayed with an aqueous acetone

solution of test compound as for preemergence tests. The

plants were returned to the greenhouse and held under

intermittent high-intensity light conditions for 10 to 14

days, after which the herbicidal efficacy of the compound

was assessed. Table 4 lists results collected in post-

emergence tests with compounds of the present invention.

For herbicidal application, the active 1,3-dioxanes

of this invention may be utilized in diverse formulations

including the agricultural adjuvants and agricultural

carriers to produce the herbicidal compositions contem-

plated herein. The herbicidal compositions contain be-

tween about 0.01% and 95% active 1,3-dioxane together

with between about 4% and 98.5% agriculturally acceptable

carrier and between about 1% and 15% surface active agent 9. S"by weight. As is well-known in the art, the formulation

and mode of application of a toxicant may affect the

activity of the material in a given application. Thus, a co•

compound of this invention may be formulated as an emulsi-

g 20 fiable concentrate, as a granule of relatively large

particle size, as a wettable powder, as a solution, or as

any of several other known types of formulations, depending S.

on the desired mode of application.

S Emulsifiable concentrates are homogeneous liquid or

paste compositions dispersible in water or other dispersant,

and may consist entirely of a compound of this invention

with a liquid or solid emulsifying agent, or may also con- tain an agriculturally acceptable liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non- volatile organic solvents. For example, a useful emulsi- fiable concentrate formulation, designated "4EC" because it contains four pounds of active ingredient per gallon of ccn- centrate (0.479 kg/liter), contains 53.01 parts of r-2-ethyl- c-4-methyl-c-5-(2-methylbenzyloxy)-1,3-dioxane, 6.0 parts of a blend of alkylnaphthalenesulfonate and polyoxyethylene ethers as emulsifiers, 1.0 part of epoxidized soybean oil as stabilizer, and as solvent 39.99 parts of petroleum distil- late having a high flash-point.

Granular formulations are particularly useful for aerial

distribution or for penetration of a canopy of foliage. Use- ful granular formulations may be of several types. Impreg- nated granules are those wherein the active ingredient is

applied to large particles of an absorbent carrier, such as

an attapulgite or kaolin clay, corncobs, expanded mica, etc.,

normally in the form of a solution in a solvent. Surface-

coated granules may be produced by spraying the molten

20 active ingredient onto the surface of a generally nonabsor- Sbent particle or by spraying on a solution of active in-

gredient in a solvent. The core may be watersoluble such

as a prilled fertilizer, or insoluble such as sand, marble *chips or coarse talc. Particularly useful is a granule

Swherein a wettable powder is applied as a surface coating

to a sand or other insoluble particle such that the

wettable powder may be dispersed on contact of the granule

-46-

I with moisture. Granules may be produced by agglomeration of dusts or powders by compaction rollers, by extrusion through a die or by use of a granulating disc. Granular formulations may vary widely in concentration, with useful formulations containing as little as 0.5% or as much as of active ingredient.

Wettable powders, also useful formulations for both

pre- and postemergence herbicides, are in the form of finely

divided particles which disperse readily in water or other

dispersants. The wettable powder is ultimately applied to

the soil or to the undesired plant growth either as a finely divided dry material or as an emulsion in water or other S liquid. Typical carriers for wettable powders include

fuller's earth, kaolin clays, silicas and other highly ab-

sorbent, readily wet inorganic diluents. Wettable powders *6 normally are prepared to contain about 5% to 80% of active

ingredient, depending on the absorbability of the active

ingredient and on the absorbency of the carrier, and

usually also contain a small amount of a wetting, dis- persing or emulsifying agent to facilitate dispersion.

Typical wetting, dispersing or emulsifying agents

used in agricultural formulations include, for example, the

'i alkyl and alkylaryl sulfonates and sulfates and their sodium

salts; polyethylene oxides; sulfonated oils, fatty acid

esters of polyhydric alcohols; and other types of surface-

active agents, many of which are available in commerce.

The surface-active agent, when used, normally comprises from 1% to 15% by weight of the herbicidal composition.

These formulations may be applied without further

dilution or as dilute solutions, emulsions or suspensions

in water or other suitable diluent. The compositions may

be applied to the area wherein control is desired by

spraying onto the undesired vegetation or onto the surface

of the soil in the case of liquid compositions or by distri-

bution from mechanical equipment in the case of solids. The surface-applied material may also be blended into the upper layer of soil by cultivation, or left as applied, as is

V. appropriate to gain the optimum results with the particular

treatment.

The active herbicidal compounds of this invention may

be formulated and/or applied with insecticides, fungicides,

nematicides, plant-growth regulators, fertilizers, and other agricultural chemicals. In applying the active com-

pounds of this invention, whether formulated alone or with

other agricultural chemicals, an effective amount and con-

centration of 1,3-dioxane are of course employed. The amount 9ee

constituting an effective amount is variable, but generally,

a uniform application of between 0.1 and 9 kilograms per

hectare is effective, for example, 0.28 to 4.48 kilograms

per hectare.

r7lAl01 (1) LN72

*0 00. 0 Q 0 0 0 0 o 0 0 000 to,6 0 .0 0 4

Table 1 Preemergence Herbicidal Activity of 4-Substituted-l,3-Dioxanes

Compound Plant Percent kill at indicated rates of application in kil-)grams/hectare of Example Species 0.28 0.56 1.12 2.24 4.48 8.96

Lima Bean 0 0 10 60* Corn 100 100 100 100 100 Wild Oats 100 95* 100 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0* 0* Crabgrass 100 100 100 100 100 Nutsedge 0 0 0 7 5*

Lima Bean 0 0 0 40 Corn 100 100 100 100 100 Wild Oats 40 95 95* 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 10* 0 Crabgrass 100 100 100 10G 100 Nuts edge 75 25 50 75'r 100

III Lima Bean 0 0 0 10 Corn 100 100 100 100 100 Wild Oats 10 90* 95* 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 Crabgrass 100 100 100 100 100 Nutsedge 0 0 40 80 100 *Plants not dead were severely damaged and not expected to live.

0* se See 6, S S 00 US Oe MS Sc. S (S -55. *S S S 0

5 0 S

Table 1 Preemergence Herbicidal Activity of 4-Substituted-l,3-Dioxanes

Compound Plant Percent kill at indicated rates of application in kilograms/hectare of Example Species U z t 0.56 1.12 2.24 4.48 8.96 Lima Bean 0 0 10 60* Corn 100 100 100 100 100 Wild Oats 100 95* 100 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0* 0* Cr abg rass 100 100 100 100 100 Nutsedge 0 0 0 75* Lima Bean 0 0 0 40* Corn 100 100 100 100 100 Wild Oats 40 95* 95* 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 10* 0 Crabgrass 100 100 100 100 100 Nutsedge 75 25 50 75* 100 III Lima Bean 0 0 0 10 Corn 100 100 100 100 100 Wild Oats 10 90 95* 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 Crabgrass 100 100 100 100 100 Nutsedge 0 0 40 80* 100 *Plants not dead were seveijely damaged and not-expected to live.

66 e 6 6 00 66 6 6 6 *eo 64 o 6 6*e 466 6 66 6 4 6 4 0 6 6 64 46

Table 1 (Cont'd)

0.28 0.56 1.12 2.24 4.48 8.96

IV Lima Beans 0 0 0 0 0* 0* Corn 70* 100 100 100 100 100 Wild Oats 20 40 80* 100 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 60* 100 Crabgrass 100 100 100 10.0 100 100 Nutsedge

XIi1 Lima Beans Corn Wild Oats Lettuce Mustard Crabgrass

Xv Limna Beans Corn Wild Oats Lettuce Mustard Crabgrass Nutsedge

*Plants not dead were severely damaged and not expected to live.

6* S S S 4~ S *5 5 C See 5* 00 5 C *4

Table 1 (Cont'd)

0.28 0.56 1.12 2.24 4 .48 8.96

Lima Beans 0 0 0 0 0* 0* Corn 7Q* 100 100 100 100 100 Wild Oats 20 40 80* 100 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 60* 100 Crabgrass 100 100 100 100 100 100 Nutsedge

XIII Lima Beans Corn Wild Oats Lettuce Mustard Crabgrass

Lima Beans Corn Wild Oats Lettuce Mustard Crabgrass Nutsedge

*Plants not dead were severely damaged and not expected to live.

5. 55 S SS o 0 S s S See S 00 C so f

Table 1 (Cont'd)

0.28 0.56 1.12 2.24 4.48 8.96

Standard Li.ma Beans 0 0 0 for Corn 0 70* Comparison Wild oats 0 0 Lettuce 0 0 Mustard Crabgrass 100 Nutsedge

*Plants not dead were severely damaged and not expected to live. **r2Ety--mtylc5(2-methylbenzyloxy) 3-dioxane.

Sg *g. 0 C C S S S Ce. S *SS* C S. j 0005 V V

Table 1 (Cont'd)

0.28 0.56 1.12 2.24 4.48 8.96 Standard L~ima Beans 0 for Corn Comparison Wild Oats Lettuce 0 Mustard 0 Crabgrass 100 Nutsedge 0

*Plants not dead were severely damaged and not expected to live. **r-2-Ethyl-5methyl-c5(2-thylbenzyloxy),3dioxane.

Table 2

Extended Evaluation of Preemergence Herbicidal Activity of 4-Substituted 1,3-Dioxanes

Kill at Indicated Rate of Compound Plant Application in kilograms/hectare of Example Species 0.28 0.56 1.12 2.24 4.48

Lima Bean 0 0 0 0 0* Corn 0 100 100 100 100 Wild Oats 0 0 20 50 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 0* Crabgrass 90* 100 100 100 100 Soybean 0 0 0 0 0 Cptton 0 0 0 0 0 Morning glory 0 0 0 0 0 Sesbania 0 0 0 0 0* Barnycrdgrass 20 70* 70* 100 100 Giant Foxtail 30 70* 100 100 100 Powny Brome 0 0 20 40 S. Sicklepod 0 0 0 0 0 Prickly Sida 0 0 0 0 0 S S Wheat 0 0 0 0 Sorghum 0 20 70 100 100 9 9 Oats 10 50 80* 80* 100 S. Barley 60* 100 100 100 100 Sugarbeet 0 0 0 0 0* Tqmato 0 0 0 0 0 S Rice 80* 100 100 100 100 .5 Safflower 0 0 0 0* Peanut 0 0 0 0 0 Rape 0 0 0 0 0

Comparison Lima Bean 0 0 0 4.. Standard A Corn 30 100 100 WiLd Oats 20 40 S Sep Lettuce 0 0 0 9 Mustard 0 0 0 S 5 Crabgrass 50 100 100 *r 0 Soybean 0 0 0 S Cotton 0 0 0 Morning glory 0 0 0 Sesbania 0 0 0 Barnyardgrass 30 100 100 9a Giant Foxtail 50 70 100 Downy Brome 0 40 100 Sicklepod 0 0 0 Prickly Sida 0 0 0 Wheat 0 0 0 Sorghum 0 100 100 Oats 20 70* 100 Barley 80* 100 100 r I--

Table 2 (Cont'd) Extended Evaluation of Preemergence Herbicidal Activity of 4-Substituted 1,3-Diox4nes

SKil- at Indicated Rate of Compound Plant Application in kilograms/hectare of Example Species 0.28 0.56 1.12 2.24 4.48 Sugarbeet 0 0 Tomato 0 0 Rice 100 100 Safflower 0 0 Peanut 0 0 Rape a0 0 Lima Bean 0 0 0 0 0* Corn 30 100 100 100 100 Wild Oats 0 40 70* 100 100 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 Crabgrass 70* 100 100 100 100 9 Soybeans 0 0 0 0 0* Cotton 0 0 0 0 0* 9 0 5 Morning glory 0 0 0 0 0 Sesbania 0 0 0 0 0* 9 Barnyardgrass 30 50 100 100 100 9 Giant Foxtail 20 30 50* 100 100 Downy Brome 0 0 0 50 Sicklepod 0 0 0 0 0* Prickly Sida 0 0 0 0 0* Wheat 0 0 0 0 Sorghum 0 40 70* 90* 100 Oats 50 70 80* 100 100 Barley 50* 100 100 100 100 94 Sugarbeet 0 0 0 0 0 Tomato 0 0 0 0 0 Rice 80* 100 100 100 100 Safflower 0 0 0 0 Peanut 0 0 0 0 0 Rape 0 0 0 0 0* Comparison Lima Bean 0 0 Standard B Corn 30 100 Wild Oats 0 Lettuce 0 0 Mustard 0 0 Crabgrass 70* 100 Soybeans 0 0 Cotton 0 0 Morning glory 0 0 Sesbania 0 0 Barnyardgrass 70 Giant Foxtail 50 Downy Brome 30

Tablqp 2 (Cont'd)

Extended Evaluation of Preeuvirgence Herbicidal Activity of 4-Sp~bstituted 1 ,3-Diox4nes Kill at Indicated Rate of Compound Plant Appliction in kilograms/he ctare of Example Species T M8 059 7.12 2.24 4.46

Sicklepod 0 0 0 0 0 Prickly Sida 0 0 0 0 0 Wheat 0 0 0 0 Sorghum 0 0 0 0 Oats 0 0 0 40 Barley 0 30 50 80* 100 Sugarbeet 0 0 0 0 0 Tomato 0 0 0 0 0 Rice 0 0 30 50 100 Safflower 0 0 0 0 0 Peanut 0 0 0 0 0 Rape 0 0 0 0 0

III Lima Bean 0 0 0 0 0 ::Corn Oats 0 10 100 30 100 30 100 70 100 100 .4.Wild

::Lettuce 0 0 0 0 0 Mustard 0 0 0 0 0* faCrabgrass 100 100 100 100 100 Sobas0 0 0 0 0 nCotton 0 0 0 0 0 Morning glory 0 0 0 0 0 Sesbania 0 0 0 0 0 Barnyardgrass 20 90* 100 100 100 Giant Foxtail 50 9Q* 100 100 100 Downy Brome 0 0 20 30 Sicklepod 0 0 0 0 0 Prickly Sida 0 0 0 0 0* Wheat 0 0 0 0 *Sorghjum 0 0 0 0 Oats 30 50 70* 80* 100 aBarley 30 50 100 100 100 Sugarbeet 0 0 0 0 0 Tomato 0 0 0 0 0 Rice 50 100 100 100 100 aSafflower 0 0 0 .0

Rape 0 0 0 0 O

Comparison Lima Bean 0 0 0 0 0 Standard C Corn 0 0 0 30 100 Wild Oats 0 0 0 0 Lettuce 0 0 0 0 0 Mustard 0 0 0 0 0 Crabgrass 50 50 80* 100 100 Soybeans 0 0 0 0 0

Table 2 (Cont'd)

Exten~ded EvaluatiQn Qf Preemergence Herbicidal Activity of 4-Substituted 1, 3-Dioxanes

Kill at Indicated Rate of Compound Plant Aplcat ion i~n kilograms/hectare of Examnple, Species 1.2 2.24 4.48

Cot ton 0 0 Morning glory 0 0 Sesbania 0 0 Barnyardgrass 20 Giant Foxtail 100 100 Downy Brorne 0 Sicklepod 0 0 Prickly Sida 0 0 Wheat 0 0 Sorghum 0 Oats 0 0 Barley 0 100 0 Sugarbeet 0 0 00 Tomato 0 0 0

0000 0 Rice 50 00 Saf flower 0 0 0 0 Peanut 0 0 .0 Rape 0 0 00 0 S.. S Comparison Lima Bean .0 0 0 0 o 00 .0 Standard D Corn 0 0 30 100 00 0 Wild Oats 0 0 20 Lettuce 0 0 0 0 Mustard 0 0 0 0* Crabgrass 0 60 100 100 Soybeans 0 0 0 0 000 Cotton 0 0 0 0 S. 0 Morning glory 0 0 0 0 000 Sesbania 0 0 0 0 Barnyardgrass 30 40 70* 100 0 05 Giant Foxtail 0 0 60 o *o Downy Brome 0 0 20 S icklepod 0 0 0 0 Prickly Sida 0 0 0 0 Wheat 0 0 20 Sorghum 0 0 20 Oats 0 20 70 100 Barley 50* 70* 100 100 Sugarbeet 0 0 0 Tomato 0 0 0 0 Rice 30 50 100 100 Safflower 0 0 0 0* Peaput 0 0 0 0 Rape 0 0 0 0*

Table 2 (Cont'd)

Comparison Standards: A. c-is-2-Ethy'L-5'-(2-fluorobenzyloxy)-l,3-dioxane. B. cis- 2-Ethyi-5- (2-me thylbenzyloxy) ,3-dioxane. C. cis-2-Ethyl-5-(2-chlorobenzyloxy)-1l,3-dioxan e. D. r-2-Ethyl-5-methyl-c-b-(2-methylbenzyloxy)-,3- "Jioxane.

*Plants not dead were severely damaged and not expected to live.

1111.25 '4

MICROCOPY RESOLUTION TEST CHIART OF STANDARDS-1963-A BUREAU NATIONAL

i

6 *03

I *5 *74 B a 3 lee a 0 a S. *66 S 0 0* S a a a., 5 0 00

Table 3

Preemergence Herbicidal Activity of 4-Substituted-1,3--Dioxanes

Percent Kill At 8.96 Kilograms/Hectare Compound of Lima Wild Example Beans Corn Oats Lettuce Mustard Crabgrass Nutsedge

V 0 100 100 0 0 10-0 -0 0 100 100 0 0 100 10c0 VII 0 100 80* 0 0 0 100 VIII 100 0 0 0 100 IX** 100 70 0 0 100 0 0 X** 100 100 0 0 100 0 xI** 100 90* 0 0 100 100 20 100 80 0 0 100 0 XVI 60 100 70 0 0 100 60 100 95* 0 0 100 100 20 0* XVIII 100 80* 0 100 100 XIX 100 100 50 100 0 100 XX 100 100 0 0 100 0 100 XXI 100 100 0 0 100 XXI I 60* 100 100 0 0 100 XXIII 100 100 100 0 0 100 XXIV 100 100 0 0 100 XXV 0* 100 100 0 0 100 100 XXVI 100 10P0- 100 0 0 100 100 XXVII 100 100 100 0 0 100 100 XXVIII 10-0 100 100 0 0 100 MXIX 60 100 100 0 100 0 XXX 0 100 100 0 0 100 0 XXXI G- 100 100 0 0 100

0O 0 *Os 66 0 6 e 6 6 6 0*66 0O* 66 6 .6 0 6 *666 6 6 6 6 6 *6 06 6

Table 3

Preemergence Herbicidal Activity of 4-Substituted-1,3-Dioxanes

Percent Kill At 8.96 Kilograms/Hectare Compound of L ima Wild Example Beans Corn Oats Lettuce Mustard Crabgras s Nuts edge

V 0 100 100 0 0 10-0 0 0 100 00 0 0 100 100 VII 0 100 80* 0 0 0 100 VIII 0 100 0 0 0 100 IX** 0 100 70 0 0 100 0 0 100 100 0 0 100 xI** 0 100 90* 0 0 100 100 XI* 0 100 80 0 0 100 '0 100 70 0 0 100 100 95* 0 0 100 100 XVIII 60 100 80* 0 0* 100 100 XIX 0 100 50 100 0 100 xx 100 100 100 0 0 100 0 XXI 100 100 100 0 0 100 XXII 60* 100 100 0 0 100 XXIII 100 100 100 0 0 100 XXIV 100 100 100 0 *0 100 XXV 0* 100 100 0 0 100 100 XXVI 100 100 100 0 0 100 100 XXVII 100 100 100 0 0 100 100 XXVIII 100 100 100 0 0 100 XXIX 60* 100 100 0 100 0 XXX 0 100 100 0 0 100 0 XXXI 0 100 100 0 0 100 0

.0 00 00* *0 *055 0 g* S 0 0 0000 SB. *0I 30 8* ~35 080 B BB** 0 0 B 0. 8

Table 3 (Continued)

Preemergence Herbicidal Activity of 4-Substituted-1,3-Dioxanes

Percent Kill At 8.9.6 Kilograms/Hectare Compound of L ima wild, Example Beans Corn Oats Lettuce mustard Crabgrass Nutsedge

XXXII 0 100 90 100 0 XXXIII 0 100 95 100 0 XXXIV-A 0 100 100 100 0 XXXIV-B 0 0 0 0* XXXV 40* 100 100 100 0 XXXVI 40* 100 100 1.00 100 XXXVII 0 60 0 100 0 XXXVIII 0 100 95 100 XXXIX 0 100 95* 100O 0 XL 0 100 100 100 0 XLI 20 100 95 100 XLII 0 100 30 80* 0 XLIV 0 0 0 0 XLV 0 0 0 0 XLVI 0 0 0 0 XLVII 0 0 0 0 0 XLVIII 80* 100 40 100 100 XLIX 60* 100 80 100 100 L 0 100 95 100 100 LI 40* 100 50 100 100 LII 0 0 0 *0 LIII 0 0 0 40 0 LIV 0 0 0 95* 0 LV 0 0 0 0 0 LVI 20 100 100 100 0

0e 0* 0 0g. 000 .0 00 0 0 0 9 0 0 .0 0 009 .0 000 000 00 0 0 so 0 0 00 0 0000 6; 0 0 e 0 00 0

Table 3 (Continued)

Preemergence Herbicidal Activity of 4-Substituted-l,3-Dioxanes

XXXII 0 100 90 0 0 100 0 XXXIII 0 100 95 0 0 100 0 XXX IV-A 0 100 100 0 0* 100 0 XXX IV-B 0 0 0 0 0 0* XXXV 40* 100 100 0 0 100 0 XXX VI 40* 100 100 0 0 100 100 XXXVII 0 60 0 0 0 100 0 XXXVIII 0 100 95 0 0 100 XXXIX 0 100 95* 0 0 100 0 XL 0 100 100 0 0 100 0 XLI 20 100 95 0 0 100 XLII 0 100 30 0 0 80 0 XLIV 0 0 0 0 0 13 XLV 0 0 0 0 0 0 XLVI 0 0 0 0 0 XLVII 0 0 0 0 0 0 XLVIII 80* 100 40 0 100 100 XLIX 60* 100 80 100 100 L 0 100 95 100 100 LI 40* 100 50 100 100 LII 0 0 0 0 LIII 0 0 0 40 0 LIV 0 0 0 95* 0 LV 0 0 0 0 0 LVI 20 100 100 100 0

Y 0* 4.9 0 0 0t 00 4 00 a 0 ~00 .0* 0 0 5.0 *0 0 a 0 a 0 0 00 0 a *g

Table 3 (Continued)

Preemergence Herbicidal Activity of 4-Substituted-1,3-Dioxanes

LVI I 0 100 100 0 0 100 0 100 100 100 0 0* 100 100 LVIII LIX 0 100 10 0 0 100 0 LX 0 100 20 0 0 100 0 LXI 0 100 90* 0 0 100 100 LXII 0 100 70 0 0 100 0 LXIII 0 100 95* 0 0 100 0 100 100 100 0 100 100 U LXIV LXV 0 100 95* 0 0 100 0 LXVI 0 0 0 0 90 0 0 0 0 0 0 0 0 LXVII 0 LXVIII 0 0 0 0 10 0 0 0 0 0 0 80* 0 LXIX 0 LXX 0 0 0 0 80* 0 LXXI 60* 100 100 0 70 100 0 LXXII 0 100 100 0 0 100 0 L XXIII 100 100 100 0 0 100 0 LXXIV 60* 100 100 20 0* 100 LXXV 0 100 100 0 0 100 100 LXXVI 0 100 80* 0 0 100 LXXVII 0 0 0 0 0 100 0 LXXVIII 0 100 100 0 0 100 LXXIX 100 100 0 0 100 100

9* *7gg e.g Ce S. 6 S C 0 0 C.- *g* C 0 0 gO *C 0 S S C S *q C.

Table 3 (Continued)

Preemergence Herbicidal Activity of 4-Substituted-1,3-Dioxanes

Percent Kill At 8.96 Kilograms/Hectare________ Compound of Lima Wild Example Beans Corn Oats Lettuce Mustard Crabgrass Nutsedge

LVI-I 0 100 100 0 0 100 0 LVIII 100 100 100 0 0* 100 100 LIX 0 100 10 0 0 100 0 LX 0 ioa 20 0 0 100 0 LXI 0 100 90* 0 0 100 100 LXII 0 100 70 0 0 100 0 LXIII 0 100 95* 0 0 100 0 LXIV 100 100 100 0 100 100 0 LXV 0 100 95* 0 0 100 0 LXVI 0 0 0 0 0 90 0 LXVII 0 0 0 0 0 0 0 LXVI II 0 0 0 10 0 LXIX 0 0 0 80* 0 LXX 0 0 0 0 80* 0 LXXI 60* 100 100 70 100 0 LXXII 0 100 100 0 100 0 LXXIII 100 100 100 0 100 0 LXXIV 60* 100 100 0* 100 LXXV 0 100 100 0 10 0 100 LXXVI 0 100 80* 0 100 LXXVII 0 0 0 0 100 0 LXXVIII 0 100 100 0 100 LXXIX 0 100 100 0 100 100 a 0* 0* a a *9 0 S *0 S a a a 0 *gg S 0 0 0~ *a 0 0 0

Table 3 (Continued)

Preemergence Herbicidal Activity of 4.-Substituted-1,3-Dioxanes I.

LXXX 0 100 100 0 0 100 LXXXI 0 100 95 0 0 100 LXXXII 0 100 95* 0 0 100 LXXXIII 0 100 95* 0 0 100 100 LXXXIV 0 100 100 0 0 100 LXXX V 0 100 100 0 0 100 100 LXXX VI 0 100 100 0 0* 100 100 LXXXVII 0 '100 90 0 0 80 0 LXXXIX 0* 100 100 0 0 100 0 XC 0 0 20 0 0 30 0 XCVII 0* 100 95* 0 0 100 XCVIII 40 100 100 0 0 100 XCIX 40* 100 95* 0 0 100 100 C 0* 100 100 0 0 100 CI 0 0 0 0 0 90 0 CII 0 0 0 0 0 80

Plants not dead were severely damaged and not expected to live.

Results3 at 4.48 kilograms/hectare.,

6. S .6

0 0e 00. 6 10" 0 *0~ 0 a 6

Table 3 (Continued)

Preemergence Herbicidal Activity of 4-Substituted-1,3-Dioxanes

Percent Kill At 8.96 Kilograms/Hectare Compound of L ima Wild Example Beans Corn Oats Lettuce Mustard Crabgrass Nutsedge LXXX 0 100 100 0 0 100 LXXXI 0 100 95 0 0 100 LXXXII 0 100 95* 0 0 100 LXXXIII 0 100 95* 0 0 100 100 LXXXIV 0 100 100 0 0 100 LXXXV 0 100 100 0 100 100 LXXX VI 0 100 100 0 100 100 LXXXVI I 0 100 90 180 0 LXXXIX 0* 100 100 100 0 XC 0 0 20 30 0 XCVII 0* 100 95* 100 XCVIII 40 100 100 100 XCIX 40* 100 95* 100 100 C 0* 100 100 100 CI 0 0 0 90 0 CII 0 0 0 80

*Plants not dead were severely damaged and not expected to live.

*Results at 4.48 kilograms/hectare.

Table 4

Postemergence Herbicidal Activity of 4--Substituted-1,3- Dioxanes

Compound Percent Kill at 8.96 Kilograms/Hectare of Lima Corn Wild Lettuce Mustard Crab- Example Bear, ___Oats grass

1 0 30* 0 20 0 100

II0 70* 0 20 10

II0 0* 0 100 40* 100

IV 0 70* 40 0 0

V 0 0 50 0 100

C. VI 0 0 30 0

C VII 0 0 20 0 0 0 U

VIII 0 0 20 0 0 0 a

XIII 0 0 0 0 0 0 S *ee S XV 0 0 0 0 0 0 S. S. S S

*Plants not dead were severely damaged and not expected to live. S. S 0*S S.

S..

a S.

S S SO..* S

Claims

FMC 4308 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:

1. A compound of the formula:

R6 R2 0 -OH 0 -CH 2 R

R 2a0--CH R

4

characterized in that V, R 2is hydrogen, alkyl, haloalkyl, alkoxyalkyl,

~.:cyanoalkyl, or phenyl;

Rais hyrgn n aand R 2taken together may represent a divalent polymethylene radical of 2 to 6 car~bon atoms, and so form a spiro structure; Ris alkyl, haloalkyl, or cyanoalkyl;

R 5is hydrogen or alkyl; R 6is hydrogen, alkyl, haloalkyl, or cyanoalkyl; r *R is phenyl, furyl, pyridyl, thienyl, or phenyl with one or two nn-hydrogan substituents selected from the group consisting of chloro, fluoro, and methyl; and in that -OCH 2 Rr bears a cis-relationship to R 2other than hydrogen.

2. The compound of claim 1 characterized in that 2 R is hydrogen, alkyl, haloalkyl, or cyanoalkyl;

R 2ais hydrogen; 4 R is alkyl, haloalkyl, or cyanoalkyl; 5 R is hydrogen or alkyl;

R is hydrogen, alkyl, haloalkyl, or cyanoalkyl.

3. The compound of claim 2 characterized in that R is R alkyl; R is hydrogen; and R is hydrogen or alkyl.

4. The compound of claim 3 characterized in that R 2 is S. 5 hydrogen and R 6 is hydrogen. 0

The compound of claim 3 characterized in that R 2 is S S alkyl and R 6 is hydrogen. OS

2 6. The compound of claim 3 characterized in that R is S 5* haloalkyl and R 6 is hydrogen.

7. The compound of claim 3 characterized in that R 2 is 5. S S.. cyanoalkyl and R 6 is hydrogen. 6*

0 S. 8. The compound of claim 3 characterized in that R 2 is

0 alkyl and R 6 is alkyl. S

0S~r

9. The compound of claim 2 characterized in that Rr is 0

phenyl or phenyl with one or two non-hy4 dogo substituents

selected from the group consisting of chloro, fluoro,

and methyl.

The compound of claim 9 characterized in that R 4 is

alkyl; R 5 is hydrogen; and R is hydrogen or alkyl.

-63-

I mi II

11. The compound of claim 10 characterized in that R is

hydrogen and R 6 is hydrogen.

12. The compound of claim 10 characterized in that R is

alkyl and R6 is hydrogen,

13. The compound of claim 10 characterized in that R is

haloalkyl and R 6 is hydrogen.

14. The compound of claim 10 characterized in that R 2 is

cyanoalkyl and R 6 is hydrogen.

15. The compound of claim 10 characterized in that R is

alkyl and R is alkyl.

16. An herbicidal composition characterized by an herbi-

cidally effective amount of a compound of claim 1 in

S admixture with an xtder.

17. A method of preventing and destroying undesired plant Oe-

growth characterized in that there is applied to the locus 0* o. to be protected an herbicidally effective amount of a

compound of claim 1.

18. The method of claim 17 characterized in that the locus

to be protected is a field planted with soybeans.

19. The method of claim 17 characterized in that the locus

to be protected is a field planted with cotton.

The method of claim 17 characterized in that the locus

to be protected is a field planted with peanuts.

-64-

-I

21. The mbth~d of claim 17 characterized in that the locus

to be protected is a field planted' with wheat.

22. Process for preparing a compound of the formula:

R6 t R2 0-CHL f 0 CH, Rr

I/0

R 2a 0-CHR

in which

R 2is hydrogen, alkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, or phenyl;

R 2ais hydrogen; and R 2aand 11 taken together may

:**represent a divalent polymethylene radical of 2 to 6

carbon atoms, and so form a spiro structure;

see R 4is alkyl, haloalkyl, or cyanoalkyl;

5. R is hydrogen or alkyl;

R 6 iL. hydrogen, alkyl, haloalkyl, or cyanoalkyl; Rr is phenyl, furyl, pyridyl, thienyl, or phenyl R

with one or two Ron-hy."oqe~ substituents selected

from the group consisting of chloro, fluoro, and methyl; and

-OCH 2 R rbears a cis-relationship to R 2other than

hydrogen; characterized pef-e.rabl.y in that a substituted

hydroxy-l,3-dioxane, of the formula: 6 R R2 01-CR OH

C C

R 2a 0 -CR in which the hydroxy radical bears a cis-relationship to R 2 other than hydrogen, is treated in a solvent with alkali metal base to form the corresponding alkali metal alcoho- late, which is then reacted with arylmethyl or heteroaryl- methyl chloride or bromide, Rr-CH 2 -Cl or Rr-CH 2 -Br, and the product is separated from the reaction mixture.

23. The process of claim 22 in which the alkali metal

base is a sodium compound.

24. Process for preparing a compound of the formula: 6 R

R O CH O CH R *2 C C 2a R O CH R 14

in which 2 R is hydrogen, alkyl, haloalkyl, alkoxyalkyl,

cyanoalkyl, or phenyl; R 2 a is hydrogen; and R2 a and R 2 taken together may

represent a divalent polymethylene radical of 2 to 6

carbon atoms, and so form a spiro structure;

R 4 is alkyl, haloalkyl, or cyanolakyl;

R 5 is hydrogen or alkyl;

R 6 is hydrogen, alkyl, haloalkyl or cyanoalkyl;

R r is phenyl, furyl, pyridyl, thienyl, or phenyl

with one or two substituents selected from the group

consisting of chloro, fluoro, and methyl; and

?,ALI 66 No. 27867/77 l Proposed: 18/6/80

-OC 2 R bears a cis-relationship to R 2other than

hydrogen; characterized in that threo-2-arylmethyl-l, 3-diol

of the formula 6 R

HO CH O CH Rr

C

HO CH

0* 0 0 1-4 *0

0* 0 0 2.s reacted with a carbonyl compound R 2R 2aC=O, or its S*

*0 0 acetal, in the presence of an acid catalyst, and the *00

0S 0 product is separated from thce reaction mixture. 0@ 0

*0e* *00* 0@ 0 0* DATED this 18th day of June, 1980. 0 00 0e 0 0000

FMC CORPORATION By its Patent Attorneys

CLEMENT HACK CO.,

Fellows Institute of Patent Attorneys of Australia.

67 No. 27867/77 Proposed: 18/6/80