DE1567038A1 - Weedkillers - Google Patents

Description

DR.-INO. WALTER ABITZ DR. DIETER MORF Patent Attorneys

β MQnctwn 27, Plenxenaurtrofle 28 Phone 483225 and «$ 441 • legrams ι Chemlndus Munich

7. Dexeeber 1965 2405-9 / 10-0

E. I. DU PONT DE NBMOUHS AND COMPANY 10th and Market Street ", Wilmington" Delaware 1989 &, V. 8t, A.

Weed killers

The invention relates to a new Klaee »ton UrÄOilen and the weeds containing ae

The Uracile according to the invention lay calibrated by the

(D

R,

represent »in what

BATH ORIGINAL

• 31.

2405-9 / 10-0

XIf- an oyoloimino group alt 2 bi · 14 Kohltaetofffttoata

and old max. 3 heteroatoms * l * tt X oxygen or sulfur,
S ₁ is hydrogen, chlorine, bromine, fluorine iodine _t "litro, alkyl having 1 to 4 Xohltattoffmtoeta, alkoxy old 1 x 4 bi lohlenstoffatonen, Hydroxyatthyl ODTR Alkoxyattnyl old

2 bit 5 carbon atoms,
B ₂ alkyl alt 1 bi · 3 Xohltärkoff Ätoata and

Hydrogen or alkyl alt 1. bi · 3 carbon atoms ,. the proviso that E ₁ and R ₂ aiteinandtr la fora tob) _n can be purified, where η equals 3, 4 or 5

old

Herbiiid compounds are known to be often used in fora «in ·· ^ • rbisid equivalent Bale ·· or a corresponding addition compound or inee corresponding loaplaxderlvmt ··, including the tinea odtr anderttt fubertitunf · - or Baad * habungsadvantage tu get, dta · DtartLrat gtftn $ b «* dtr Ttrbinding ale eoloher lcann. Ia tnteprtohtlidtr Vtl "t dta from the present Irfindung also Alt Salat ι dlt tion compounds and the Koaplext der Üsaollt." Taiat foratl (1) old encompassed, the eioh au "Ltnleba ··" unA * 4to & m "fhaltta laaeen and a similar htrbiaidt W «W» f nit ■ elbit taifaltta · ' \ ' ■ '"j."

ν.

Btv

, ρ

8aa _fl t _r A ^ dlUoiitTtt% iait «^ i

24O5-9 / 1O-Ö.

the Üraeilen de * lormtl (1) can be formed, one

Baatn

Sodium hydroxide Potash hydroxide Lithium hydroxide Oaloiiinhjdroxid ^ Magnteiviehjdroxid Barix «hydroxide Strontium hydroxide Sieen (III) - * hydroxide Manganese hydroxide Quaternary Aamoniu Hydroxide Prieärt, etkundür «and t« rtittr) t Ärnint Htttrooyolieoh Aain

Guanidiu

Anidint

Phenol

Krtiol "

laphthol
Acids

Halogenitrtt Btniotic Acids Mineral sculptures Organic sulfonic acids Halogenated ", aliphatic acids

- ^ i:,; , OJ09826 / 2O33 ORIGINAL BATHROOM - - 3 -

2405-9 / 1Ο-σ ^

Halogenated, aryloxyallphatleohe 8 acids Organic, aliphatic and aromatic acids.

On the basis of their economic effectiveness as ale herbalism, uracils are referred to the forael (1), in which X Sauerateff and R _? Let hydrogen, while the R ₁ substituent on balocene (ie 01, Br, F or J) or methyl beaohxiakt iet and the ring Hl · - contains a total of 1 Stioketoffmtoa.

Of the derivatives of the Urqile of the forael (1), fOv are the Purposes' of the invention salsa precautions, the old latriua, potassium and lithium can be obtained as cations »since this salsa lelohts are soluble in water and frozen in the form of valuable solutions can be.

In the formula (t) the Oyoloiaino-Orupp · Al- In der Position of the üraoilring remnants such as

009126/2033 - 4 -

BATH ORIGINAL

2405-9 / 10-G

O N

R ₄ -H H-

(CH3),

0- /

³ Y

CH,

CH ₃

include, where R "alkyl" biait 1 fci "4 or -CH ₂ CH ₂ OH and y is equal to 0 bl" % , Vi * henden BtBreibung eriohtiiij ^v i _t Ui.jifi.sst £ $ r

iainc "used in äem hler ^ n Bi> a © 3 /, t ^; ο *

? t> n

BATH

2405-9 / 10 = G.

A well-suited procedure for restoring the original roll gemass the invention is illustrated by the following equations:

(2) OO Beneol ♦

/ \ Bäurekaflyaator

(K-NHCNH ₂ + CH ₃ C-CH ₂ COOC ₂ H ₅

0 OH, 11 t 3

3 \ - IrHCNHC-CHCOOC ₂ H ₅

(3) / \ 0 CH,

3 H - 3THCTITE Fc-CHCOOO ₉ H ₁ .

HO ₁

Sas bti equation (2) al starting material used seal carbaeid can according to Ann., 221, 904 (1893) or Ber., J ^ t 4477 (1902).

The appropriately substituted urea is treated old

000826/2033 ORIGINAL BATHROOM ⁶ T

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a ß-ketoester or an exercised ß-xatotste », dtr substituted with radicals such as alkoxy, fluorine or alkyl an acidic catalyst at reflux In a solvent, from which water is continuously removed. Haoh distance An ethanolic solution is given to all of the water Base, such as sodium methoxide, added. Haoh a few minutes of itchfluas the reaction mixture is cooled and washed with W & sessv tx ~ traced. When the aqueous layer is acidified, it secretes » desired product in crystalline 3? © rm.

That at the end of the first stage, i. after sowing the water, the product obtained is a ·. TJr «ldoverbiiiduDLge ~ Mf & n kftzm this connection, if desired, isolate and purify, but for the implementation of stage 2 neither condition is an advantage.

It is assumed that these abovementioned £ jr * iöoY compounds according to the following equation in a £ er both tautomeric Fο neon or both are present;

CH ₃ -C-CHOOOC ₂ H ₅

NH?

HH- / sί \ HH- Jf S

vL / v_ /

BATH ORIGINAL

2405-9 / 10-G

Uracile according to the invention, which is in the 5-8 division "it halogen, Nitro and hydroxymethyl are substituted and are easy to use according to the standards used in the literature for related compounds, general methods.

In the case of chlorination, Mutohaftl allows τοη to be used Sulfuryl chloride instead of chlorine a more comfortable way of working

The 5-Nitro-Uräoile of the finding can duroh directly Nitration of uroils which are uneubstituted in 5-3 positions,

will be obtained:

* Ό -nc

4 (T ¹ SI ^ Nj ₄ H ₉

As explained by equation (7), the üeeeteung ron uracils that are uneubstituted in the 5-position »alt For · -

0098 ^ 21 ^ 2033 BATH

2405-9 / 10-ö

aldehyde to uracile », which identifies in the 5-6 division a»? methyl group substitute!

/ 7>

- I.

As the following shows ßleiohung "can ran the formula (1) _t is in the 1-position slkyloubatä sw ^ xt eiaä"'A urn etching a Dialkyleulfatea with a Sfatriiameals eiqes subatituiertöE Uraoil-Auegangeaate ^ ale maintaining · »ι

The 'i-alkyl oracile can auoh naoh d «? will receive »ι

Br

^< r?

nar

S 0 S S? f / 2

BATHROOM 0RK3INAL

'Bit Kttallsalse according to the Brfinduag will be paid for after the king

Methods, with duroh dissolving the free ureoile in a watery

Any or non-aqueous solution aiadeetene an equiaolar amount of a bast or a basic 8alsts old daa gtwttnsohttn cation, obtained · 2. B. A Vatriuasals can be obtained by dissolving the urea in water, which contains an equiaolar amount of sodium hydroxide "The water can then be isolated from the solution by means of permanent removal of the water." Oils la Vaster unleashed uroilsal are best divided up, loaded into an aqueous solution, an alkaline salt, dee üraoila or an aqueous solution of a water-soluble Selees dee lietalle treated. _vy

o.uattary adraonluasalae of the terbonds of the ferael (1) are divided up, while aaat da · substituted tRraeH old of an entipre ^ headen Quaternary Inaoniuahydroxiduaeetst, 9 »die ··,. Äydroxidt la general in solution sur the disposal steven _t

the Uastteung aa most comfortable in the same Löeungeaittel through * · geftihrii. If you want the solution-free outlet, you can . clean it easy by removing the solvent tube exsaXtea

_; On the other hand, the Aamonluasalie of the Uracile can be derived from the corresponding latriusealsen la einta trecka "s \ _f iaertea

: LÖsyngsaitt ^ I, like foluene or xylene, are divided up · Ksa then gives the corresponding · qnartary AnnioniwiaaTtgeaid nater · ttifetm üad, mm, nptwenOig, ltiohtea Irhitsea. 5a · »I

? | i OOI8 e / v ^ÄO33: 1

BADORIßlNÄt

2405-9 / 1Ο-β

forming sodium halide is filtered off, whereby Ammonium ale of uracile remains in solution * Wens gfwttaeoht » you can get the approval rating eleven matures Sale by ft '; fci «mx« ß β ta I »8» Solution medium, preferably in a vacuum, is received.

Addition compounds of the uracils of the lOrael (1) with Lewin bases, like amines, laaeen eich received, lndeoi iaan Mixes portions of a corresponding Uracile and a Baee · Dae Öeaieoh is under HUhr · » Mählioh heated, before a clear Sehmels «Torlie« t »B # ia cool down crystallizes the traditional bond «Dae Produkt kann

then from a solvent such as Bensol, Cyclotutier, ί1ΐ * ο ~

methane or acetonitrile, can be crystallized *

Complexes of the uracils of the formula (1) with a Lewie-Baee, such as phenol, can be obtained when the uracil and the phenol melt in a ratio of 1 i1 to 1 imaanaeis. Let SiOH also obtained indett the Eeekti ons participants mn in the same Terhältnie asuosmmen In a «« solvent such Hitrometha "or" (Jemlioh vm lemon than and cyclohexane triggers "The Arbeitebedingungra *> m & insulation methods comply with the above for M & ltlonsiverisin & tsnige ear levels «

The Uraoiiderlvate according to the invention, as well as the. Uraciles of the formula (1) and their salts, addition compounds

0 0 9 8-2.6 / 2033

- 11 BAD ORIGINAL

156703S

«405-9 / 10-0.

and complexes, have a lot of excellent herbicidal activity ·

;.; ■ ■ ■ - "'■ ' ■ · .- ·. ■■. ·" -. ^; ■: ■■ · ■ ■■ ·

Ytnii "an" It duroh Sprltien men dta casserole "a la doping"!

- ■■ ■■ - ■■ ■ ■■ · ■ .. ■■■■■■,. . · ..;

ton approx. 2 x 45 kg of active ingredient (approx. 2 to 40 pounds / aor) applies »iseigen ti ·,« ine beaondtr · efficacy bti dar Ba-

Raging of annual and perennial deaths, such as AfTOpyron repene, Sorghua halepense, Cynodoa daotylos and Oyperue, 4ie on aerial tramway, on industrial terrain or in or on the outskirts of Hatalandes farmersohaftlioh own farms, boys and girls are good enough Annual Graeee and broad-leaved weeds after and dead the emergence duroh Bpriteen in a dosage tob ttva 1/4 Ui 3 1/2 kg / na (about 1/4 to 3 pounds / aore). XLa further, more important applications, the compounds geaäee the discovery let the control of a wide spectrum of weeds and Bueohpflanaen on induction terrain and Bieenbahnohotter gate and near the emergence, whereby aaa with dosages τοη about 5 1/2 to 45 kg active substance Aa (about 5 to 40 Pound / Acr «) arbai-

The compounds according to the invention are rorsugaweiee with Auxiliary substances, modifying agents or thinners. (hereinafter generally referred to as inert carriers) with pesticides brought into dta preparation form. The sub-line facilitates the handling and often reratärkt eo ^ ar the herbal effect · Such herbal preparations become in the form of powdered solids, granules, sFellets or liquids

/ 2033 • · ig -.

BATH ORIGINAL

2405-9 / 1 (MJ

Liquid resources, such as solutions or dispersions a%? Bonds according to the invention in a "liquid Löiiyngeaittel, such as the netebaren powder contain al" Κοηβΐΐΐο & ΐ: detergent one or more surface-active agents in sufficient quantity _t u * <* ae the compounds sown of the invention in water or oil leioht dl ^ pergable ga maohen. The term "surface-active agent" includes wetting agents, dispersing agents, suspending agents and granulating agents.

In the manufacture of the anti-inflammatory agents, surface-active agents are generally applied in concentrations of about 1 to 10 percent. With big * & N "3igen _e wi # 0.3 to 6 parts / Uraoil are rasohende advantageous irgebnieee received but unusual and tibet ~. Solohe means mt gen stronger herbixide Vlrksamkel'l as el · due to represent activity of the components in separate - fine ** · su would be expected.

Powder or dust according to the 3rfin4unf »

also with modification with a »surface-active Mltttl«,

are obtained by using the active ingredient ®i%

ten Festetoffträgerii mieoht «B« r Gewiohtta »^ til <t @ s Vflr« t-ff »does not change with the type itnä W« lae, In de? $ * a üitt # l räfgi-

brach ": werdtn noll _s bftjpiet * i3« 3p 1 » all & swiimfc « tw & 0 _t > b :; '* 1 » vom Oewioht dt»

BAD ORIGINAL «p tf ·

84P5-9 / 1O-0 ...

Also know the weed control agents of the invention Contain two or more of the uracils. You can aueltslloh ία the ürftoilen also contain other, well-known herbiides.

Su ilen known herbiiids, which old according to the uroils Irf indun «Y can be purified, belonged

3- (3,4-Diohlorphenjl) -1,1-dieethyluritol 3- (4-chlorophenyl) -1,1-dimethyl urea

5- (4-chlorophenyl) -3HMthöxy-1,1-dineth7lharnatoir 5- (3,4-I) icblorphen3rl) -1-n-butyl-iHMthylurjtoff

3- (4-0hlorphenjl) -1- «ith <rty-1-ethyl urea 3- (3,4-Diohlorphenjl) -t, 1,3-tri »ethylharnitofi 3- (3,4-Dihlophenyl) -1, t-diethyl urine

Urine substances can old dta üraoilen leaa «· the B * fiaftmf be mixed in proportions of 1 t 4 bit 4 ι 1, where ·! a Verbaltniβ from 1 t 2 to 2 ι 1 beTortu ^ l will ·

JBttbatitttlerta triasine BAD ORiQtNM.

2405-9 / 10-0

2-methoxy-4,6-bi8 ~ (ieopropyla »ino) - 8-triasin

2-chloro-4,6-bi- (ieoprcpylamino) -B-trift £ ia

This · Triasine can use the Uraoilec genäes the Rrfisäirag in units Sound 1 t 4 to 4 * mixed one "with a Veriiaitnie of 1 ι 2 ι his 2 1 is preferred *

Phenols

MnItro-o-eek.-butylphenol and «a SaXi © Fentaoblorophenol and its Salse

These phenols can be mixed with the ftraoilea geuäise £ #> * Bäfi ^ dtiag in Shares of 1 ι 10 ble 20 t 1 are rented ^ where «in ¥« ir » never lasts from 1 t 5 here 5 »1 door is sucked ·

Carboxylic acids ~ derivatives

These carboxylic acids and derivatives can be mixed with the uracils » of the invention In the following proportions are borrowed ι

0 0 98 ^ 6/2033 BAD ORIGINAL

2,3,6-friohlorto «ne« «alur · and lh» · 8 * 1 ·· 2,3 »5, i-tttrtehl« p * «MO« elur · and you · 0 * 1 ·· 2 ^ tht ^ - $ _# M-tri «hlorb« ie © o * ur · and lh «· 8 * 1 ·· 2-M« tbox7-) _v 6 «dlehlor ^« ttee «« lur · and her · 9Hb & no- £ * 5-Alolilocfe «nao« Bllttr · and you · β ·! «· 9 ~ * ltro * 2,5 ^ iehlorb«! Mo «alui * · and you · 8 ·! ··

2 ₉ 4-9iohlorph «Bmqr« i «lt« ttiuM and her · S «1m and 2» 4,5 ^ riohl <»rph« i «S] r« t * ic * iar · and her · 8ml · · and B «t« r

and you · 8 ^ ·· and

2> (2 ₉ 4i5-friohlor | li «noz7) -propifnallur · and her · BaIm« nd

2> (2 ₉
Ärtir

4- (2 ₉ 4-Diohlorphtnoxy) -tartt «rfttttr · and you · 8 · 1μ and

4- (2 ^ l «tliyl-4 - <» hlorph * nexy) -butt »raur · and you · 8Om and Isttr

Kitohu & i U Terhlltni · 1 t 16 bi · θ t I ₉ τοτ «α« · ν · 1 ·· 1 ι 4 Ui

ι 1.

lUeolning Ui Twrtitltni · 1 · 4Ml 4 »1t yctujünüji i ι 5

frlohlor «a« if »* ttr · and you · 8 ·! ·· TUtohunf U T «rh & ltni · 1 ι β Η · β? ι 1>. T ^ rwfittt ·· 1t 1

bi · θ ι 1. ■■■ · ■■■. ' ■ " . '■ £ & ■ # ■ > - /

O St 1/2 0 / i 0 * 3 3 'C

• - ιβ -

BATHROOM ORIQlNAt -

2405-9 / 10-0

2,2-Diohlorpropionic acid and its safe Mixing in the ratio 1 s 4 bia 8 t 1 «YormgtVela * 1 t f

up to 4 ϊ 1

N »N-Dipropyethiol carbamic acid, ethyl ester D-propyl-5, H-dipropylthioloarbamate '

H-propyl-N-ethyl-n-butylthiooarbanate *

Mix in the ratio 1J 2 to 24 * 1, preferably 1: 1 to 12 »1.

N-phenylcarbamic acid · »isopropyl ester N- (m-chlorophenyl) -oarb'asdn« lar « _v isopropyl ester N- (m-chlorophenyl) -oarbaninstor ·, 4-obloro-2-butynyl ester mixture in a ratio of 1 t 2 to 24» 1 »Rorwis wise 1 t 1

up to 12: 1.

2,3,6-TriohlorphtnyltssifAure and its · Salae mixture in the ratio 1 ~ 12 to 8 ~ 1, TOV «ttgfWciet i % 4 to 4 ~ 1.

Maleinsfturehyäraiid

Mixture in the ratio 1 J 2 to 10 ι 1, "YOrmtmtlf · 1 * up to 5 ι 1.

00 $ 826/2033 - tr »-

BATH ORIGINAL

2405-9 / 1 (M?

The following strings can old the primeval lines of burning To be rented in the following proportions.

Calcium propylar sonate Dinatrius H monomethyl arsonate Octyl-dodecylamraoniueaethylarsonate

Mixture in a ratio of 1: 4 to 4 ι 1 »preferably 1 l 2 ble 2: 1,

Sodium areenite
Mix in the ratio 1: 5 to 40 ι 1, Torsugsvtls * 1 t 4

up to 25 % 1..

Lead arenate CaIoium Arsenate

Nleohung in a ratio of 150: 1 to 600 t 1, torso wsls * l 1 to 400: 1. '

Sodium tetraborate, hydrated, Sodium metaborate latrium pentaborate

Polyboronate

ünrafflnlertss Boratelneral, like Borasoa Mieohung Ib ratio 6 ι 1 to 1500 ι 1 »TorsufMrtl · · 3 ι 1

bit 1000 ι i. '. ·

009126/2033

BATH ORIGINAL

2405-9 / 1O-ö . * 0 '

Sodium chloride

Mixing in a ratio of 2 t 1 to 40 ι 1, previously «1 t 1 up to 20 t 1.

Ammonium sulfamate

Mix in a ratio of 1: 1 to 100 * 1 »Yorsöfavtlee 1 ι 1 up to 50: 1.

Other organic herbigids

5,6-dihydro- (4A, 6A) -dipyrido- (1,2-A.2S1 »-Ö) pyrazinium dibromide

Mixing in the ratio 1 t 20 to 16 ι 1, from trueirweiüe 1 ι 3 up to 5: 1.

3 amino-1,2,4-triazole

Mix in the ratio 1: 20 to 20 ι 1, before * ugtw * iie 1 ι 5 up to 5 ϊ 1.

3,6-boundoxohexahydrophthalic acid "
Mixing in the ratio 1 j 3 to 20 t 1, Torsugvw ·! ·· 1 t 2

up to 10 * 1. ·

Hexaohloroacetone

Mixing in the ratio 1 t 2 to 16 t -1, advantage · * ·! ·· 1 t 1 to 8 ϊ 1.

BATH ORIGINAL

2405-9 / 10-β

Diphenylacetonitrile

Ή , N-dimethyl-α, β-diphenylaoetaaid

N, N-Di-η-pro py 1-2,6-dinltro-4-trifluoromethylanllln

N, N-di-η-propy1-2,6-dinletro-4-ethylaniline Mleohung in the ratio 1 ι 10 bit JO ι 1, torsufmiee 1 ι 5 bit 20 ι 1.

O- (2,4-dichlorophenyl) -0-methyl-leopropylpho «phox« aldo ~ thiat

2,3 »5,6-T # trachloroterephthaletur», Mleohung Im Verbaltni · 1 t 4 bi »2OtI, vorufml · · Ii 3

up to 15 ι 1st,

Others aubatltixlert Uraoil

The tJraoile can be compared with other developed Ur * oiXeB Ia dm the following proportions.

3Oyolohexyl-6 <-eethylur * oil 3-cyolohexyl-6-ethyluraoil 3-0yolohexyl-6-eelc.-btttyluraoil 3-Norl) ornyl-6-diethyluraoll 3-Oyolopentyl-6 - «# thylurÄOll 3-oyolohexyl-6-propyluraoil

Mleohung in the ratio 1 % 4 tie 4 * 1 »fOreufeveiee 1 ι Ms 2 t 1.

009826/2033

- 20 ORIGINAL BATHROOM

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3-Cyolohexyl-5,6-triaethyXtnuxaoiX 3-eek, -ButyX-5 ₁ 6-triaethyXinurmolX 3-isopropyl-5 · 6-triBethyX «auraeiX 3-Ibopropyl-5t6-tetraa» ethylenur * oil 3-1oopropy1-5 »6 -pentaa "thyl * nur" oil

Mitigation in the ratio 1 χ 6 to 6 ι 1, Yorsufw ·! ·· 1 ι 4 Ms 4> 1.

3-Cyclohexyl-5-broiBttraoiX 3-CyclofcexyX-5-cliXorureoiX 3-isopropyl-5-tronufeoil 3-aek.-ButyX-S-bromuraoiX 3-3ek.-Butyl-5-ohloruTÄCil 5-bromo-3-8ek-butyl-6-methyXuraoil 5-3rom-3-eek-butyl-6-niethyXuxaoiX, Ia-8 «X * 5-ChX or-3-eek.-butyl-6-etthyXurmotl 5-bromo-3-tert-butyX-6- «ethyXu« ioiX 5-chloro-3-tert-butyl-6-methyXureoil 5-bromo-3- (1-ethylpropyl) -6-ethyXuraoiX 5-chloro-3- (1-ithyXpropyl) -6- «tthyXu» ülX, 5-bromo-3-isopropyl-6-methylur * oil 5-chloro-3-isopropyl-6-methyluraoiX 5-Bromo-3-oyoloh # xyl »tthyl-6-ffl #thylur» ox

3-Cyolohexyl-5-niethoaty-6-methylur * ox 3-eek-butyl-5 »6-diarthyluraoil

009926/2033

BATH ORIGINAL

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3-eek.-Butyl-6-methyl-5-nitroure, oil 3-Cyoloheacyl-5 _f 6-dimethyluraeil 5-Broffl-3-cyclohexyl-6-a * thyluraoll 5-chloro-3-phenyl-6-ethyluraoil

Mixture in Vernaltnie 1 t 6 to 6 t 1, failure · «·! ·· 1 ι 2
to 2 ι 1.

3-Isopropyl-1-trlohlorethylthylthio-S-br 6 hy

3-Cyolohexyl-1-trlohlorttethylthio-3-o 6 tttraall

3-1-bopropyl-1-aoetyl-5-bro 6 · hyl «raoH ^H
3-Ibopropyl-1'-triohlor «» thylthlo-5-ehloir 6 -thylwwtoll

Mining in the ratio 1 ι 4 ble 4 »1, venmgpvtfi ·· 1 l 2

up to 2: 1.

Me the following example, in which eioh partially

information, if not otherwise specified «on da QwieM blefce»

serve to further broaden the

Example 1

Sin öeaitoh of 126 parts 1- (toahydro-1 - »« eelnyl) fcTB »toff _t 104 parts Xthylaoetoaoetat, 4 tail ·» p ^ foluolwni tmaton * «afl 1300 parts of toluene is 20 hours backflueebeÄ ** daX% tw« b * i mm

008126/2033 - 22 -

BATHROOM ORIGINAL> ^r

2405-9 / 10-0

in this period 11.3 part · Waiter in one original · after Dean-Stark collects. The reaction mixture is cooled and there is 220 parts of a 29% solution of atrium methoxide in methanol added and resumes the RÜokfluas treatment for 3 hours, cools the mixture back to its old age «pour the egg into 1000 parts of water and stirs vigorously. Mari now separates the aqueous solution from the organic schioht from "extracted there" Hatrlums as Um 3- (Haxahydro-1-a «epinyl) -6-.methyluraoil · with 500 parts of water and waeoht the united "earthy 8ohiohten with 250 tellan Methyl chloride. Duroh acidification of the aqueous bohiolites with 95 parts of concentrated hydrochloric acid precipitate the 3- (hexahydro <»1-aaepinyl) -6-mthyluraoil au ··

The product is filtered off and washed alternately with 600% water

flushed. . .

The crystallization from acetonitrile gives the pure 5 ~ (Haxa

hydro-1-azepiny.1) -6-methjlurapll _#

If, in the above example, instead of Ithylaoetoaoetates and 1- (Heiahydro-1-aBepinyl) urea fs equivalent amounts of the Entepreohenden β-ketoesters and ureas are used The following uraciles in table I are similar in catfish

obtain"

009826/2033 - 23 -

BAD CWlGiNAL

a b β 1 1 β Ι

Beiepitl ß-Ietoeater- Reactions

Subatit.-Harnetoff reaction customer

Prodturt-Urell

itbyl-butyro-a-fluoromoetate

1- (H «xahydro-1-azepinyl) 6-ethyl-3- (hexahydro-1- -urea asepinylj-uraoll

* S-MLttor-S-ihexaliydro-i-

a 8fplnyl) -4 ~ propylngaell

5,

ι * 6

o-thoxymortate

IO 11 12

3- (H * xahyilro-1

5,

oraoll

I) -

Ail

l) -

Β «1 · ρ1 · 1 S-Ketoeoter-

Respondents

14 15 16 17 18 19 20 21 22 '25 24

Ethyl propionate Ethyl aceto-a-fluoro acetate Ethyi-aceto-a-methyl acetate Ethyl aceto-a-butyl acetate Ethyl aceto-o-nethoxyacetate Xthyl-aceto-a- "butoxyacetate

2-Carboethoxyeyolop «ntanone

Ithyl-ÄO "to -" - * thyl * acetate

Subatit.-urea reactants

Product tJracil

1- {4-morpholino) urea

1- (1-piperidino) urea

6 "-Xthyl-3- (4- morpholino) uracil

5-fluoro «6-methyl-3- (4-morpholino) uracil

5, 6-M.methyl-3- (4-morpholino) »uracil

5-butyl-6-methyl-3- (4-mofpholino) «uracil

5-methoxy-6-methyl-3- (4-morpholino) uracil

5-butoxy-6-ethyl-3- (4-aorpholino) -uraoil

3- (4-Morpholino) -5 »6-trimethyleneuracil

6-methyl-3- (1-piperidino) -uraoil

ro

■ P * O UI 1 vO

5HuorMihy
peridino) -utaoil

no) -uracil

5-ethyl-6- »ethyl-3- (1-pip ^ ^ ridino) -uraoil ^

5-Btttyl-6-e * tliyl-5- (1-plp • - q ridino) -uracil oj

example β-Kstoeeter-
Reaction lone participant Subetit.-Harnetoff-
Reaktlonet recipients * 25th Xthyl-aceto-a-methoxyacetate 1- (1-Pi perldino) -ur-
etof f 26th Xthyl-aoeto-a-ethoxyacetate η 27 Xtby 1-aceto-a-propozyacetat η 28
ψψΛ 2-carbo & thoxyoyοίοpentanone η > ο
σ _ο 29
O ·> 2-carboathoxyoyelohexanone n 2-carboethoxyoycloheptanone η Ethyl butyl acetate 1- (1-pyrrolidinyl) -
urea «A
32 Xthyl-aoeto-a-fluorooetate N 33 Xthyl-aeetea ethyl acetate n 34 Ethyl- "oeto-"> * thylaoetat ■ .35 Xthyl-aoeto-o-propylaoetate « 36 Xthyl-aoeto-a-eetljoxyaoetat

Product uroil

5-methoxy-6- * iethyl-3- (1 -pi- f peridino} -uraoil ^ r

5-Xthoxy-6-methyl-3- (1-pipe- f ridino) -uraoil c

6-methyl-3- (1-piperidino) -5-propoxyuracil -

3-O-piperidino) -5,6-trieethyleneuraoil

3- (1-piperidino) -5 _t 6-tetramethyleneuraoil

51 ö-pentamethylene- ^ (1 -piperidino ) -urao il Vi

6-Propy1-3- (1-pyrrolidinyl) -_ uraoil

5-Huor-6-methyl-3- (1-pyrrolidinyl) -uraoil

5 ₉ 6-Dieethyl-3- (1-pyrrolidinyl) -uraoil

6-IIIethyl-5-propyl-3- (1-pyramidinyl) -uraoil

5-methoxy-6-ethyl-3- (1-pyrro £ j lidinyl) -uraoil

37 38 39 ♦ 0

«Ο
co

σ>

ο
«Ο

42 43 44 45 46 47 48

β-ketoester reactants

Substitute -Harnet of f respondents

Product uracil

Xthyl-aceto-α-isopropoxyacetate 1- (1-pyrrolidinyl) urea

2-carboethoxycyclopentanone ^R

2-Carboethoxycyclohecanon Ethyl acetoacetate ethyl aceto-a-ethyl acetate Xthyl-aceto-a-fluoro-acetate ithyl-aceto-a-fluoro-acetate Ethyl aceto-a-methyl acetate

1- (1O-phenothiazinyl) urea

1-CDihydro-1,3,5-aithiasisi ~ 5-yl) -urea

1 - (1-aziridinyl) urea ey5pp pyrrolidiny1) -urac il

3- (1-pyrrolidinyl) -5> 6-trimethyleneuraoil-

3 ~ (1-pyrrolidinyl) -5 »6-tetra» methylenuracil

6-methyl-3- (10-phenothiazinyl) "=" uracil

5,6-dimethyl-3- (dihydro-. 1,3 »5 ~ dithiazin-5 ~ yl) uracil

3- (Dinydro-1,315-dithiazin-5-y 1) ^A 5-fluoro-6-iaethyliiracil

3- (1-Aziridinyl) -5 ~ fluoro-6-methyluraoil . . -.

3- (1-Aziridinyl) -5,6-dimethyluracil .

Xthyl- * o «to-α-methoxyacetate 1- (2-ethyl-1-aziridinyl) urea

Ethyl propion-a-methyl acetate "

ithylacetoacetate

1- (1 _f 2,3t 6-tetrahydro.1-pyridyl) urea

S-methoxy-e-methyluracil

6-ethyl-3- (2-ethylaziridinyl) -5-methyluraoil

6-methyl-3- (1,2,3,6-tetrahydro-1-pyridyl) uracil

Ethyl-eoeto-a-ethoxy-acetate 1- (4-ethyl-1-pipera-

zinyl) urea

5eyy3 (4-ethyl-1-piperazinyl) -uraoil

8405-9 / 1 (KO £ J ₁

Ni KV i "i fci

1 «Si

. If ii fc « Pr * ¥ H l. * 5»

ft *! With fl. '

«4

! IH! ι ff || || '4 v, jj

«Λ4» ΙΛ4 »ΙΛ« - IAv UW Λ * Λ '

♦ • β

CSl «Η

- ^ Οι
Il

Φ Φ

H H

ι «?

7 *

H 4 »

J,

S 5

I i

4 »

■ $

4 »<♦» 4 »4 ·

Φ Φ · ·

I f

I!

4 »4» 4 »4» P

R 5; a

009826/20 3 ORIGINAL BATHROOM.

L

ItI!

R S R 8

Ö-ketoeater respondents

Subatit.-urea = Respondents

Product uracil

Ul

ethyl-aeeto-cc-methyl acetate

Ethyl aeeto-a-methoxyacetate

1 ~ (2 ~ methyl-1-piperidino) urea

ο S3 Ethyl-aceto-a-isopropoxy-
acetate It S? 64 Ethyl acetο-α-fluoroacetate η 0982
3 ORIGII 65 Ethyl propionate 1- (1-piperazinyl) urine
material > 66 ithyl acfito-a-lautyl acetate M. 67 Xthyl-aoeto-a-athoxy acetate η 68 Ethyl acetoacetate 1- (2-methyl-4-pyrosoli
1-yl) urea t 69 Ethyl aceto-a-ethyl acetate α 70 Ethyl-aceto-a-fflethaxyacetate π 71 Ethyl-aoeto-o-fluoroacetate it 72 Xthyl-aeetoaeet & t 1- (tetrahydro-1,4-thi €
zin-4-y1) urine

5,6-dimethyl-3- (2-methyl-1-piperidino) uracil «B

5-methoxy-6-methyl-3- (2-methyl-1 -7 pi peridino) -uracil

5-13opropoxy-6-methyl-3- (2-methyl-1-piperidino) uracil

5-fluoro-6-methyl-3- (2-methyl-1-piperidino) uracil

6-ethyl-3- (1-piperazinyl) uracil

5-butyl-6-methyl-3- (i-pipe- * razinyl) uracil

5- thoxy-6-ethyl-3- (1-piperazinyl) uracil

6-Hethyl-3- (2-aethyl-4-pyrazolin-1-yl) uracil

5-ethyl-6-methyl-3- (2-methyl-4-pyrazolin-1-yl) uracil

5-methoxy-6-methyl-> 3- (2-methyl-4-pyrazolin-1-yl) uracil

5-Plucr-6-methyl-3- (2rmethyl- ^w 4-pyrazolin-1-yl) uracil

6-methyl-3- (tetrahydr0-1,4-co thiazin-4-yl) -uraeil \

Β * 1 * ρ & «1 6-Xetoeater-

Respondents

Subetit. -Urea reactions partisans

Product uracll

VJl

ittoyl-propion-Ki-methyl acetate 74 75

: 'W 77

79 80

81

82

Ethyl-aoeto-a-methoxyacetate

ithyl-aceto-a-fluoroacβtat

ethyl-etceto-st-H diethylaoetate ithylaoetoacetate lthylacetoacetate ithyl-aeeto-a-Bethozyaeetat-

Ethyl-aoeto-O-ethyl acetate

1- (tetrahydro-1,4 ^ zln-4-yl) urea

1- (dihydro-1,3,5-dioxa- «yn-5-yl ) urine

1- (1,2,3,4-Tetra5iydro-2-ieochlnolin3fl) -urea

1 - / ^ "(2-B * drorjäthyi) -1-piperaeinylT-harafltoff

6- & thyl-5-methyl-3- (tetra- * v hydro-1,4-thiaein-4-yl) - ο uracil ι

5-methoxy-6-methyl-3- (tetrahydro-1,4-thiazin-4-yl) -uraoil

5-fluorine-6-methyl-3- (tetrahydro-1,4-thiazin-4 ^ yl) -uraoil

3- (Dihydro-1,3,5-dioxazin-5-y1) -5,6-diaethyluracil

3- (Dihydro-1,3 x 5-dioxazine- < 5-y1) -6-methyluraoil

6-methyl-3- (1,2,3,4-tetrahydro-2-ieoquinolinyl) uracil

5-methoxy-6-ethyl-3- (1,2,3, 4-tetrahydro-2-leodninolinyl) uracil

5Ithyl3Ziiy0yy) 1-piper * »Iyl7-6-methyluracil

532? 4lyyy) 1-piperft «inyV-6-HMthyiuraoil

Example S-Ketoeeter- Rtalcti onet participants

83

84 Xthyl-aceto-a-methoxy acetate

85 86

S 87 m

ο »88 κ»
S β9 ft *

90 91 92

93

Ethyl-aceto-cc-methyl acetate Xthylaeetoaoetat Α-fchylaoetoacetate

Ethyl-aoeto-a-fluoro-acetate

2-carboethoxyoyclopentanone

Subeti t. -Harnatof f - = ■ Lesson participant

Product uracil

Ethyl aceto-a-methoxyacetate

1- (1,2,3,4-tetrahydro-10-phenothiazinyl) urea

1- (Dodecahydro-10-phenoxazinyl) urea

decahydro-9-carl »a -) - urea

1- (2-methyl-4-pyrazolin-1-y1) urea

1- (Tetrahydro-1,4-thiai4l) ^ tff

1- (Dihydro-1 »3,5-dioxazin-5-yl) urea

1- / 4- (2-hydroxyethyl) -1-piperaainylZ-barnetoff

1- (2-methyl-1-piperidino) urea

5-Methoxy ^ 6-methyl-.3- (1,2,3,4-4 tetrahydro-TO-phenothiazinyl) - ^e uracil

3- (dodecahydro-10-phenoxa'-zinyl) -5-methoxy ~ 6 «isethTl-

uraeil

516-T-dimethyl ~ 3- (dodeoahydro " 10-phenoxazinyl) uracil

3- (Dodecahydro-T0-phenoxazinyl) -6-methylttracil

(y
6-methyliiracil

5lUS- (dodecahydro-9-cartiasolyl ) -6-methyluracil

ypy 5 $ 6-triBethyXe2tuxaeil

3- (Tetrahydro-1,4-thiazin-4-yl) -5, e-triMethyleneuracil

3- (Bihydro-1,3 "5-dioxazin-5-yl) -5" 6-trieethyl "nura6il

p
tiraoil

-5 »6-trimethylene-

3- (2-Methyl-1-piperidino) -5,6-triethylnaracil

Ca) OO

2405-9 / 10-0

is

«-Οι

Ύ5 YS Y

Ύ5

«- N

S Y?

σ »

7 P ft TO Sf

β 4 P as Si

Ϊ «Ρ Λ IC

t it "■ ·;

• w Ii JI Vt Sf lilt 11 III

sfl κ Ii ß ί4 ff xf It si

jilS Si JiI JiX XS U rf Jit Sfo

«» J -2

rt re ι

• * i CMl '♦ • rf · * £. ^W.

Yfl Y3 Yr Yr Y

ch o% δ ο 8

ψ- r · -f "

009826/2033

BADORIQIMÄU

2405-9 / 10-α

Example 106

Production of 5-chloro- (3- (hexahydro-1-a »epinyl) 6-methyluraoil -

8 parts of chlorine are gradually stirred in tine solution rom 22.3 Parts 3- (Hexahydro-1-azepinyl) -6-aetbylurau3il, 16 parts WM » β er for ei em ffodium acetate and 100 parts of Bieeeüg a, where during the Ohlorzusa lake the temperature is below 30 ° 0 · » willc The solution will after complete «Ghlorsuiats a stirred for another half hour at room temperature and then in 200 parts of water are poured out. The product is collected and washed with water receives.

Using an equivalent amount of the appropriate uroil reactant and the halogen, see Table II instead of 3- (hexahydro ~ 1-arepinyl) -6-nethyluraoile and The chlorine of Example 106 can be used in a similar manner receive the following 5-Halogenuraoile

BATH ORIGINAL

Table II Example Uraoll output

reaction subscriber

Amount of halogen (halogen)

Got product uraeil

107 108

109 ο 110

· Ιιι k »112

• »• 113

1U 115 116

117

6-Xthyl-3- (hexahydro-1-azepinyl) uracil

3- (Hexahydro-1-azepinyl) -6-methyluracil

6-methyl-3- (4-eorpholino) -uraoil

8.0 (Cl ₂ ) 17.0 (Br ₂ ) 17.0 (Br ₂ )

β, Ο (Cl ₂ )

6-ethyl ~ M4- * orpholino) -uraoil 17.0 (Br ₂ )

6- * tethyl-3-O-piperidino) uracil 17.0 (Br ₂ )

• 8.0 (Cl ₂ I.

1 _f 6-Dleethyl * -3- (1-piperidino) -ura «il β, Ο (0I ₂ )

Uao) - 17.0 (Br ₂ )

uraeil

1-ethyl-3- (hexahydro-1-α «epynyl) - 17.0 (Br ₂ ) 6-ethyluraoil

1,6-Dieethyl-Mt-pyrrolidinyl) - 17.0 (Br ₂ ) uraoil

VJI

5-chloro-6-ethyl-3- (hexahydro-1-; azepinyl) -uraoil

5-bromo-3- (hexahydro-1-azepinyl) -6-methyluraoil

5-Bromo-6-methyl-3- (4-norpholino) -uraoil

5-chloro-6- «ethyl-3- (4-aorphollno) -uraoil

5-BroÄ-6-ethyl-3- (4-aorpholino) -uraoil

5-Bro »-6-ethyl-3- (1-piperidino) -uraeil

5-Onlo * -6-ethyl-3- (1-piperidino) -uraeil

5-0nlor-1,6-dleethyl-3- (1-piperl- r; dlno) -uraoil

5-Bro »-1,6-di» ethyl-3- (4- «orpholino) -uraoil

5-Bro »-1-ethyl-3- (hexahydro-1 -asepjL-nyl) -6 <-aethyluraoil

5-Broa-1,6-dlMthyl-3- (1 -pyrrolidine nyl) -uracil '

Example uracil Auegangs-

respondents

Amount of halogen (halogen)

Obtained product uracil

118

119 120 121

_ 122

ο
S 123 IO

cn

ί5ΐ24

*> 125 126

127 128

129

6-propyl-3- (1- pyrrolidinyl) uracil

6-methyl-3- (1-pyrrolidinyl) uraoil

6-methyl-3- (10 «phenothiazinyl) -uraoil

3-CDihydro-1,3,5-dithiazin ~ 5 ~ yl) 6-aethyluraeil

3- (Dihydro-1,3 »5-dithiazin-5-yl) 6-methyluracil

6-methyl-3- (1-aziridinyl) urac5

1, β-iBethylS / jy (3 »2 · 2) -nonan-3-y! / - uraoil

6-methyl-3- (1,2,3,6-pyridyl) uracil

6-methyl-3- (4-methyl-1-pfperexi nyl) -uraoil

17.0 (Br ₂ )

17.0 (Bt ^ ₂ )

8.0 (Cl ₂ )

8.0 (Cl ₂ )

17.0 (Br ₂ )

8.0 (Cl ₂ )

8.0 (Cl ₂ )

17.0 (Br ₂ )

17.0 (Br ₂ )

1.7.0 (Br ₂ )

8.0 (Cl ₂ )

8.0 (0I ₂ )

5-bromo-6-pro py 1-3- (1-pyrrolidine? I) - J. uracil "*>

5 ^ Bromo-6-methyl-3- (1-pyrrolidinyl) -, L. uraoil

5-chloro-6-ffiethyl-3- (1-pyrrolidinyl) -wracil

5-chloro-6-methyl ~ 3- (1O-phenothiazinyl) -uraoil

5-bromo-3- (dihydro-1,3 »5-dithiazin-5-yl) -6-methyluracil

5-chloro-3- (dihydro-1,3,5-dithiazin-5-yl) -6-methyluracil

5-chloro-6-methyl-3- (1-aziridinyl) - ^ uracil

5-bromo-6-methyl-3- / 3-esal> ioyolo- (3.2.2) -nonan-3-y V-uracil

5-BT0H-1,
(3.2.2 O

5-BroB »-6-ethyl-3- (1,2,3,6-tetrahydro-1-pyridyl) uracil

5-ση1θΓ-6-η ·· Μΐχ1-3- (1,2,3,6-tetrahydro-1-pyridyl) uracil J ^

5HChlQr-6- «ethyl-3- ^k (4-methyl" -1-pipe-. Rasinyl) -uracil

130
131
132
133

«134

'157
Ι3β

140
141

H & lq.quantity (Halogen)

Got product uracil

3 ^ 2,5-Bi * ethjl-4- * orpholino-6- 17.0 (Br ₂ ) ■ ethyluraoll

"8.0 (Cl ₂ )

3- (9-Carta «olyl) .- 6-inetayluraell 17.0 (Br ₂ )

6- * ethyl-3- (2-ethyl-1-piperidi- 17.0 (Br ₂ ) no) -uraoil

6-Ärtliyl-V (i-plp «ra« liiyl) -ur »oll 17.0 (Br ₂ )

17.0

6-ethyl-3- (2-ethyl-4-pyramolln-8.0 (Cl ₉ ) 1-yl) -ttcoll ^c

6-methyl-3- (t «trmliydro-1,4-thiMln-8.0 (0I ₂ ) ⁹ 17.0 (Br ₂ )

»3,5-dioxa» ln-5-yD-

2-Hydroacylthyl) -

17 _t 0 (Br ₂ ) 17.0 (Br ₂ ) 17.0 (Br ₂ ) 5-Bromo-6-Biethyl-5- (2,5-dlae thyl-4-norpfaollno) -uraoil

5-chloro-6-methyl-3- (2,5-dla «ethyl-4 aorphollno) -nrecH

5-Brcm-3- (10-oarbarolyl) -6-methyluraoil

5-Bro »-6-ethyl-3- (2- ^ thyl-i-plp ^ ri.dino) -aracil

■ · ■

5-bron-6-ethyl-3- (i-plpera * inyl) -uraoil

5op6MHyl3
»OHn-1-yl) -oracll

eolln-1 «yl) -oraoil

5r-Ohlor-6-ethyl-3- (tetr * hydro-1 _t 4-thia «ln-4-yl) -araoil

l-3- (t «traliydro-1, 4-

& yl-3- (1,2,3,4-tetr - hydro-2-laoohi3rolinyl) -araoil

5-bit »-3- (dihydro-1,3,5-dioxaeln-5- **

3- / 4- (2-hydroxyethyl) -1-piperm-6ttalll

^T J r ac 11 — Exit titijLh

145

Ί46

147

149 Amount of halogen Obtained product uracil (Halogen)

rtethyl ~ 3 ~ (1,2,3,4-tetrehydrohthillil

3 - (Bodacfthyäro-10-phenoxazinyl) c-methyltirAcil

3— (I ^ odBcahydro — 9 — carlÄBolyl) —6— methylureoil

3- (3-Hydroxypip * rldin-1-yl) -6 - methylozmelX . ·

1 - pyrrole 1 <11 ny

6-methyl-5- (2 _t 3,5,6-tetMU »thyllf1l) ll 17.0 (Br ₂ ) 17.0 (Br ₂ ) 17.0 (Br ₂ ) 17.0 (Br ₂ ) 17, 0 (Br ₂ )

17.0 (Br ₂ ) 17.0 (Br ₂ ) 17.0 (Br ₂ )

5-Br om ~ 6-ae thy 1 ^ -3- (1,2, 3 * bydro-1O ^ phenothlazinyl) uracil

5-Broi »-3- (dodeoahydro-10-phenoxa zinyD-6-diethyluracil

5-bromo-3- (clodecahydro ~ 9-caTbazole) 6Ulil

5-Broe-3- (3-hydroxy piperidine-1 yl) -6-ethyluracil

y thyl

y uraoll

f5 _t i

nethyluraoil

2405-9 / 10-α ■ ■

BtliHltl 150

Preparation of 3- (HexaJ ^ dro-1 ^ eepinyl) -5-üydroxymetbyl- ^ tfrfti 1

Am Qetaleoh of 22.3 parts of 3- (Hexaliydro-1 - * «epinyl) -6-« etbyluraoil, 140 parts of wa μ er, 32 parts of ethyl alcohol, 6.6 parts faraformaldehyde and 2 healing barium hydroxide is erliitat, blah all components yollatindlg; are valid. The solution is drained then off and extract the surttok stay ^ de oil old Xthev The animal extract is dried over MagnealUBeuKmt and filtered and the jtther removed, whereby aan daa 3- (Hexahydro * 1-aieplnyl) 5-hydroxymethyl-6HBtth> -urmoll is obtained.

Duroh use an equivalent amount of dee eatapreohenden Vraoll-Seaktionetellnehaere according to Table III anetelle dee 5- (Hwrmhydro-1- * B * pinyl) -6-Ethyluraoile in Example 130 lmeeen eloh In a similar manner the following 5-Hydroxynethylurmoile obtain.

BATH ORIGINAL

2405-9 / 10-G

I 1

4 »

4 »

• rf
4 »

H
• Η
O

CU

I!

ι I

^β I
* ι ~

VO

ι- ι ι hi

Sh

• drf

UH • β »4

I ·

in

V 21

ΙΫ »ίτ it ·

¹ S!

ίΛ Ot ΙΛ?

Ft • Η H

H • a O CU £ 4 Oil O •H β Oi I. I:
T- I. T H H i? ■ dd 4 » 4 · « St « VO vo

r- CM

009826/2033 ORIGINAL BATHROOM,

Example uracil reactants Obtained product uracil

162 163 164 165 166 167 168

Z 169 170

3 - <$ ~ (2-hydroxyethyl) -1 -? - piperazinylj- »6-methyluracil

1,6-diethyl-3- (hexahydro-1-azepinyl) uracil

1,6-Dipropyl-3- (4-morpholino) -uraeil 1-methyl-3- (4-morpholino) -6-propyluraoil 6-methyl-3- (4-norpholino) -1 ~ propyluracil 6-methyl-3- (1O-phenothiasinyl) -uraoil

3- (Dihydro-1 _t 3,5-dithie «in-5-yl) -6-methyluraoil

3- / 3-Aeabicy olo- (3 * 2.3) -noaan-S-y ^ -eaethyluraoil

6-Me "iyl-3- _(1,2-f 3.6 tetralxydro-1-pyri dyl ·) -uraoil 5-hydroxymethyl-3- / 4 ^ (2-hydroxyethyl) -1iileothlil

1,6-diethyl-3- (hexahydro-1-azepinyl) -5- J hydroxymethyluracil ν

1,6-dipropyl-5-hydroxymethyl-3- (4 »morpholino) uracil

5-hydroxymethyl-i-methyl-3-Κ 4-morpholino) -6-propyluracil

5-hydroxymethyl-6 ~ methyl-3- (4-morpholino) -
-1-propyluracil

5-HydPOxymethyl-6-ethyl-3- (1O-phenothia-binyl) -uraoil

3- (DihydPO-1,3,5-dithiazin-5-yl) -5-hydPoxymethyl-6-methyluracil

3 - ^ - A "abicyclo- (3" 2.3) B "thyl-6-fflethyluraoll

5 ^ yxyeyleth
hydro-1-pyridyl) uraci

2405-9 / 10-α
Example 171

Preparation of 3- (hexahydro-1-azepinyl) -6-methyl- 5-nitrouraoil

In a mixture of 120 ropes of concentrated Sohulfelure and 120 parts of fuming nitric acid are long «« 45 parts · 3- (Hexahydro-1-azepinyl) -6-methyiuraoil stirred in. One stirs dae reaction mixture 15 min., The temperature below 35 ° is held, then slowly adds 500 parts of iced water and collects the product that is secreted, the old water Acid-free washed and dried, whereby Bin das 3 ~ (Hexanydro-1-azepinyl) ~ 6-methyl-5 ~ nitrourtoil receives.

In a similar way the following 5-iitroureoil can be prepared, by replacing the 5 "- (hexahydro ~ 1-aiepinyl) -6-methyluracila in Example 171, in each case an equivalent amount of one of the oil reactants listed in Table IV begins.

0098 ⁴ 2β72033

BATH ORIGINAL Table IV Example Uzwoil reactants Obtained product uracil

172 173 174 175

176 177

6-methyl-3- (4-morpholino) urac11 6-Hethyl-3- (1-pi peridino) -urac11 6-methyl-3- (1-pyrrolidinyl) uracil

6 <4-methyl-3- (4-methyl-1-piperaziny1) uracil

3 * - (2,5-Dimethyl-4-norpholino) -6-ne thyluracil

6-methyl-3- (2-methyl-i-piperidino) uracil

6-methyl-3- (1-piperaainyl) uracil

6-Methy1-3- (2-ethyl-4-pyrasolin-1-uracil

6-methyl-3- (tetranydro-1,4-thiaein 4-yl) -ar * cil

(y _t ■ ethylnrmoil «

6-methyl-Mi _f 2,3,4-tetrahydro-2 isoohiaoliayl) -urmcil ο 6-methyl-3- (4-morpholino) -5-nitrouraqil ο 6-methyl-5-nitro-3- (1-piperidino ) -uracil 6-methyl- »5-nitro-3- (1-pyrrolidinyl) -uracil

6-methyl-3- (4-methyl-1-piperaeinyl) -5-nitrouracil

3- (2,5 ~ Dimethyl-4-morpholino) -6-methyl-5-nitrouraoil

6-methyl-3- (2-ethyl-1-piperidino) -5-nitrouracil

6-methyl-5-nitro-3- (1-piperaeinyl) -. ^ uraoil * ■

6-methyl-5-nitro-3- (2-ethyl-4-pyraeolin-1-yl) -uraoil

6-methyl-5-nitro-3- (tetrahydro-1,4-thiaein-4-yl) -uraoil

3- (Dihydro-1,3 _t 5-dioxasin-5-yl) -6-ethyl- ^ itil

3Z ^ (y 6-aetnylnrmoil 6-methyl-3- (1 # 2 _t % 4-t "tr ** iyteo-2-ieoquinolinyl) -5-nitrouraoil

3- / 3- (2-Hydro3cyethyl) -1-pipera * ynyl7-6- ■ ethyl-5-nitrourmcil .

Example Uraeil reactants Obtained product uracil

184 185 186 187

O 188 Q ο
PS ¹⁸ 9 he »

190

1,6-diethyl-3- (hexahydro-1-azepinyl) uracil

1,6-Dipropyl-3 ~ (4-morpholino) uracil 1 -Methyl-3- (4-niorpholino) -6-propyluracil 6-methyl-3- (4-aorpholino) -1-propyluraeil 6-methyl-3- (1O-phenothiazinyl) uracil

3 (Dihydro-1,3,5-dithiazin-5-yl) -6-methyluracil

3- (Aziridin-1-yl) -6-methylura6ll

6-methyl-3- (112,3,6-tetrahydro _{-1-pyridyl) -uracil 1 t} 6-diethyl-3- (hexahydro-1-azepinyl) - = 5-nitrouracil

1,6-dipropyl-3- (4-morpholino) -5-nitrouracil

1-methyl-r3- (4-morpholino) -5-nitro-6-propyluracil

6-methyl-3- (4-morpholino) -5 ~ nitro-1-propyluraoil

6-methyl-5-nitro-3- (1O-phenothiazinyl) uracil

3- (Dihydro-1 ₁ 3,5-dithiazin-5-yl) -6-methyl-5-nitrouracil

3- (1-Aziridinyl) -6-methyl-5-nitrouracil £

6-methyl-5- nitro-3- (1,2,3,6-tetrahydro-1-pyridyl) uracil

2405-9 / 10-G

Example 192

Manufacture of "3 — fHexahvdro — 1 —azAnlnvl) —5 — Iodine — 6 — mathvluraoil

A mixture of 22.3 ropes 3- (Hexahydro-1-aBepi & jl) -6-methjluraoil, 100 parts of Eaeigeäure and 25 # 4 parts of iodine is under Stir gradually at 100 ° C with 7.5 parts of fuming nitric acid offset. After completing Zueata, the solution is refluxed for 1/2 hour and then cooled in an egg bath.

The excess iodine that precipitates out is filtered off and the precipitate appears diluted with 400 parts of cold water. There · in the oeaieoh Any remaining iodine is made up by adding a sufficient amount of a saturated, aqueous sodium sulfite solution to the solution To make colorless, sum iodide ion reduced.

The aqueous Gemieoh is extracted with 800 parts of methylene chloride, separates the organic layer, bison with saturated Sodium carbonate solution and then dry with magnesium sulfate.

When the methylene chloride is removed, there remains J- (hexahydro-1-aseplnyl) -5-iodo-6-methyluraoil lurUok

The following 5-iodine oils can be produced in a similar manner

009826/2033

2405-9 / 1Ο-α

hold * by replacing the 3- (hexahydro ~ 1 ~ a »« yinyl) -6 methyluraoil from example 132 % © because »an« equivalent to the uroil reaction part of other vegetables

BATH ORIGINAL

Example Uracll implementation file

sr,

ο ¹ m

195 194 195 196

197 198

• ο 199 200

201 202 203 204

6-methyl-3 ~ (4-morpholino) - «raeil 6-4fethyl-3- (i-pipepidino) uracil 6-methyl-3- {1-pyrrolidinyl) uracil

3- (4-methyl-1-piperajsinyl) -6-methyl uracll

3- (215-Bliaethyl-4 "HK> rpholino) -6-thIII

3-ί 2-methyl-i -piperidino X-6-methyluracil

6- «etfay1-3- (1-piperazinyl) uracil 6-methyl-3- (2-methyl-4-pyrejiolin-

o-i, 4-thiÄBin-

y ■ rtfaylexmoil

i »ochlnolinyl

Got product uracil

to

5-iodo-6-ae thyl-3- (4-Hoorpholino) -uracil 5-iodo-6-methyl-3- (1-piperidino) uracil 5-iodo-6-oethyl-3- (1-pyrrolidinyl) ^

5-iodo-3 ^ (4-methyl-1-'piperazinyl) -6-Biethyluraoil

3- (2.5 ~ M.methyl-4HBorpholino) »S-iodine-emethyluraoil

5-iodo-3- (2-methyl-1-piperidino) -6HB * thyluraoil iP

5-iodo-6-methyl-3- (1-pi peraeinyl) uracil

5-iodo-6-ethyl-3- (2-ethyl-4-pyra-olin-1-yl) -araoil .

5-iodo-6-methyl-3- (tetrahydro-1 _t 4-tliia2in-4-yl) - «racil

3 (y, 5
6-ethyluraoil

, 2 _r

il

5? My3 (,
i8oohinolinyl) ~ uraoil

3- (2-Bydr oxy & tny 1) -1 iodo-6-methyluracil

. Example 'uracil reactant Received product uracil

205 207

^20β

se
ι ss 210

2212

y ^ - (hexahydro-1 -azepinyl) uracil

1,6-pipropyl-3- (4-morpholino) tracil

1-methyl-3- (4-morphoün.i>) -6-pr o py 1-uracil

6-Hetliyl-3- (4-morpholino) -1 -pro pyluraeil

6-Hethyl-3 ~ (10-phenothiazinyl} -uracil

y ₁ 3 x 5-methyluracil

6- «et! Iyl-3- (1 -pyrrolyl) -uraoil

y3 ( _t 2 _t 3.6-tetrahydro-1-pyrldyl) -uracil 1, δ-diethyl ^ - (heacahydro-1 -azepinyl) -S-ioduracil

1,6-dipropyl-5-3 od-3- (4-morpholino) uracil

5-iodo-1-methyl-3- (4-norpholino) - '6-propyluracil

5-Jbd-6-iaetfayl-3- (4-morpholino) -1-propyluracil

^ - (.10-phenothiazinyl) -

uracil.

3- (Dihydro-1 _f 3,5-dithiazin-5-yl) -5-3od-6-methyluracil

5-iodo-6-methyl-3- (1-pyrrolyl) -uracil ^ £

5-iodo-6-methyl-3- (1,2 ₁ 3 $ 6-tetrahydro-pyridyl) -uraoii

2405-9 / 10-G ** '

Example 213 Preparation of 3- (fiexahydrt> -1 ^ Bepinyl) H5HwthoaEy pethyl-6-methyluraoil

A mixture of 22.3 parts of 3- (hexahydro ~ 1-aeepinyl) -6-methyluraoil, 140 parts of water, 38 ropes of ethyl alcohol, 6.6 files Paraformaldehyde and 2 ropes of barium hydroxide is 1/2 8td. while stirring to hot-flow conditions, the LöeunÄ in a bis bath, neutralized with dilute hydrochloric acid and. removes water with alcohol duroh stripping at reduced Pressure.

Ken stirs the residue with 50% methanol, removed duroh filtering the solution inorganic Salee, versetet the Solution with 1 part of chloroacetic acid gives the reactants into a bomb and heated to 125 ° 0 for 6 hours. The reaction mixture will sit for several minutes 1 fur colored carbon (activated carbon) heated, helee filtered and at reduced * pressure by stripping off the solvent, which means that 3- (Hexahydro ~ 1-aBepinyl) -5- «ethoxymethyl-6-ethyluric oil obtained.

I) The following 5-alkoxy-ylnraolle can be obtained in a similar manner by adding an amount of the 3- (He * ahydro ^ iHMi "pynyl 6-methyluraoili and methanol in example 213 elvalefi% e amount of oil oil. R. action participants and alcohol ^ e <e "ae" fabelle Π elnsetet.

000126/2033 from y

BAD ORIQtNAC

8405-9 / 10-0 y.

• Η

0 0

'4 * t

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Ιϊ if It ί% ~ ι

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BAD ORfGiMAL

ί III

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sy

Example Uraeil Realrtioneteilnelimer

224 225 226 227

§ o 228

229

μ 230

«231

232 233

Alcohol reactionary participant

Obtained a product uracil

hydro-2-ieochinoiinylj-urÄCil

3- / 4- (2-Hydpo3qr ** hyl) -1-piperazinyiz - ^ - raethyluracil

, iy> (li azepinyl) -uraeil

1,6-bipropyl-3- (ollno) uraoil

1 -Methyl-5- (4-w> rphollno) -6-propyluraoil

y propylur «ell

y3 nyl) -uracil

5-yl) 6 fcylttJEeH

hydro-1-pyrl4yl)

ΟΗ, ΟΗ Iao-

O-HgCffl

CSHvOB CH-OH

il

OB-OH

5 ^ etfaoxyiaethyl-6-ynethyl-3- (1,2,3,4-tetrahydro-2-ieoquinolinyl) -uracil

3-ZU (2-hydroxyethyl) -1 -pi perazinylj-5-ieopropoxymethyl-6-methyluracil

1,6-diethyl-5-ethoxymethyl-3- (heiahydro-1-asepinyl) uracil

1,6-Dipropyl-3- (4-eorpholino) -5 - «* k." butoxyaethyluracil

-3- (4HBorpho-

5-Hethoxymethyl-1
lino) -6-propyluraeil

5-methoxymethyl-6-methyl ~ 3- (4-morpholino ) -1 -propyluraoil

5-ethoxy "" ethyl-6-ethyl-3- (10-pheno-3- (dihydro-1,3 _t 5-dithiaein-5-yl) -5-

5- "ethoiy" # ethyl-6-ethyl-5- (1,2,3,6-. trtr »hydro-1-pyridyl) -urmcil

CJ C3O

2405-9 / 10-G
Example 234

Manufacture of IS p

A mixture of 22.5 parts of 3 ~ (Heaeahydrö-1-az®pinyl) -6-methyluracil, 350 files water and 13 files ftatriuifihydroxyd will be warmed to 45 ° 0 and stirred until the Eeetoffe eion dissolved to have. The solution is slowly added with 37.8 parts of bimtthyleulfei; added and the reaction mixture was stirred at 45 ° 0 for 1 hour. The product obtained is separated from the Waesereohioht and subjects it to air drying, whereby the 1,6-dimethyl-3- (hexahydro-i-azepinyl) -uraoil is obtained.

The following 1-alkyluracils leave eioh entepreohender way obtained by'man instead of 3- (hexahydro-1-aaepinyl) -6-methyluracils and dimethyl sulfates of Example 234, equivalent amounts of the alkyl sulfates and uroil reactants according to Table VII begins. .

- 51 009826/2033

BATH ORIGINAL

Example of Üracil reaction participants Table VII

Alkyl sulfate- Obtained product-uracil Rector member

Ii

5-chloro-6-methyl-3- (4'-morpholino) -uraeil

5-bromo-6-methyl-3- (1-piperidino) uracil

. 237 5-Xthyl-6-methyl-3- (1-pyrrolidinyl) -uraoll

238 5-chloro-6-methyl-3- (2-nethylazirldin-1-yl) -uraoll

5-3roiu-3- (iiexahydro-1 -ezeplnyl) nyl) -6-methyluraoil

3- (4-Horphollno) -5f6-trlaethyleneuraoil

3- (1-piperidino) -4-thio-5t6-trl-methylemiraoil (OH ₃ ) ₂ SO ₄
(CHj) ₂ SO ₄

5-chloro-i _t 6-dimethyl-3- (4-morpholino) uracil

5-Bromo-1-ethyl-6-methyl-3- (1-piperidino ) -uracil

-pyrro-

5-ethyl-6-ethyl-1-propyl-3- (1 lidinyl) -ure.oil

5-chloro-1 _t 6-diaethyl-3- (2-aethylasiridln-1-yl) -oraoil

5-Broa-1 * 6-dieethyl-3- (hexahydro-1-aseplny1} -uraoll

1-methyl-V (4HK) rpholino) -5,6-trimetnylenuraoil

1-methyl-3- (1-piperidino) -4-thlo-516-trleethyleneuracil

2405-9 / 10-G
Example 242

Preparation of 3- (hexahydro-1-assepinyl) -6 - methyl-4- thiouracil

Am Gemisoh of 22 parts of 3- (Hexahydro-1-aii «pynyl) -6-methyluraoil, 50 parts of phosphorus pentaulfide and 500 parts of pyridine is treated with stirring for 6 hours, rüokfluas-treated, Ken * ngt daa G - miech with reduced Druok to about a third of its original Volume and then pour it into 1000 felle Bis and water. Pie siobically resulting precipitate is separated and dissolved in 150 parts of 2 N sodium hydroxide solution and. dl · obtained solution filtered to remove insoluble impurities cu. Buroh Acidification of the filtrate with concentrated salic acid will do that 3- (Hexahydro-1-azepinyl) -6-methyl-4-thiouraoil precipitated

The following 4-thionouraoils can be used in a corresponding way Catfish are obtained by replacing 3- (H «* hydro-1-asepinyl) -6-methyluraoile of Example 242 one equivalent amount of the oil reactants according to Table VIIZ used *

BATH ORIGINAL Table VIII Example uracil reaction participant Obtained product uracil

243 244 245 246 247 248 249 250

5-fluoro-6-methyl-3- (4-morpholino) -uraoil 516-diethyl-3- (4-morpholino) uracil

5-Iaopropoxy-3- (i-piperldino) -6-methyluracil *

3- (1-piperldino) -516-trimethyleneuraoil

5x6-dimethyl-3- (4-methyl-1-piperazinyl) -uraoil

5-methoxy-6-ethyl-3- (1,2,3,6-tetrahydro-1-pyridyl) -uraoil

5-Broa-3- (hexahydro-1-asepinyl) -6-aethyluraoil

5-BroB-1.6-di "ethyl-3- (bexahydro-1-asepinyl) -" raoll

5-fluoro-6-methyl-3- (4-morpholino) -4-thiouracil . . ^

5,6-diethyl-3- (4-morpholino) -4-thio- £ uracil

5-Ieopropoxy-6-methyl-3- (1-piperidino) -4-thiouraoil

3- (1-piperidino) -4-thio-5,6-trimethyleneuraoil

516-dimethyl-3- (4-ethyl-1-piperazinyl) -4-thiouracil

5-Hethoxy-6-methyl-3- (1 »2 ₁ 3,6-tetrahydro-1-pyridyl) -4-thiouracil

5-bromo-3- (hexahydro-1-asepynyl) -6-. 5 methyl-5cl

5-Bro «-1.6-dieethyl-3- (hexahydro-1-

5-Bro «-1,6-dieethyl-3-azepynyl) -4-thiouracil

2405-9 / 10-0 5 * ;

Example 251

Production of 5 ~ bromine -) - (hexahydro-1-asepinyl) -6-methyluraoilf

A solution of 4 parts is added. latriumhydroxyd in 150 parts of water 21.7 parts of 5-Broe-3- (bexahydro-1-asepinyl) -6-methyluraoil added and the suspension is heated under stirring »zn to the dissolution effect. The water is then removed from the solution under reduced pressure, whereby the hatriuäsal of the uroile remains surttok as a white solid.

The following metal salts can be used in a corresponding manner obtained by replacing the 5-Bro «-3- (hexahydro-1-as * pinyl) -6-methyluraoila and latriumhydroxydes of Example 251 equivalent amounts of other uracils and other metal hydroxides used. The following list gives examples of typical salts according to the invention.

At s pi el

252 5-Bromo-6-methyl-3- (4-morpholino) -uraoil _f M-SaIs

253 5-Bromo-6-methyl-3- (4-morpholino) -uraoil _f I-Sala

., 254 5-Bromo-6-methyl-3- (1-ipiperidino) -uraoil, Ia-SaIs

255 5-chloro-6-methyl-3- (1-pyrrolidinyl) -uraoil, Li-SaIs

. 256 5,6-Dimethyl-3- (1-pyrrolidinyl) -uraoil, K-SaIs

257 3- (4-Morpholino) -5 _f 6-trimethyleneuraoil _f Li-Sals

. 259 5-Bromo-6-ethyl-3- (1-pyrrolidinyl) -uraoil, Ia-SaIs

009 ^ 8 ^ / ^ 2033

BATH ORIGINAL

2405-9 / 10-0
Bel-

259 5-Ohlor- € -m * thyl-5- (i-plp * rldlno) -ur * oll _f

260 5-iodo-6-ethyl-5- (1-pyrrolidinyl) -ux »oll _t la SaIs

261 5,6-Dimtthyl-5- (h «Ahydro-1-Epynyl) -4-thionuraoil,

Ha-SaIi

The following Β · 1 · ρ1 · 1 · explain the · production «id use τοπ preparations, velehe di · htrlileld «ktlt« n vtrblnüngen geattea of the Brflndiing included.

262

3- (hexahydro-1-a§eplnyl) -6-

metnyluraoil, Ia-SaIe 5 *

IatriuBlauryl Sulphate 2 %

Water 95 J *

The LOming is made, but “to the two of them

Bale · while moving in the vaseer read · Biese Lusung is suitable • loh for the rapid thinning to the desired «Entretionen.

This aqueous solution becomes very unsuccessful near the emergence elngeeetit. With 2.2 ti 3.4 kg active ingredient / h * (2 ti 3

009826/2033

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Pounds / Aor ·) in 281 1 (30 gallons) Va βaer becomes a «ttfge ~ without control of Digitaria ep ·, Aaaranthu · ep., Braesioa kaber, Seoale oereale, Stellatie ep · and Avena fatua obtain*

At concentrations of 2.2 to 4 * 5 kg Virketoff / oa (2 to 4 * 5 kg 4 pounds «) in 935 1 (100 gallon) Vaeeer receives aan old dieeer Preparation a worthwhile fight against a variety of annual and broad-leaved weeds that grow in Bangier * railroading on Sieenbahneobotter waoheen.

Example 263

Väeeriite guepention

5-bromo-3- (hexahydro-1-aaepinyl) -

6-methyluraoil 28.0 ^

Vatrlunllgnineulfonat 15 # Q 3 * Hydrated Tr Attapulglt 2.0 p Disodium oephate $ 0.8 Vatrluapentaohlorphenat 0,3 ^

Waeeer 53 »7 t

The roasted constituent parts are sifted and subjected to tin * * or eandoafalung, bit $ £ t du? Oi »e * iuiittllali · $ eU-ohengrdeee dee active substance active H & tariaXe im

"Bit" is below 5 micrcii case ^ i * - htr

BAD ORIOINAL

2405-9 / 10-G

58 ..

Suspension does not bake and can easily be washed with water diluted, very slowly settling suspension, which does not require any movement during application.

If you use this aqueous suspension for targeted spray control in a dosage of 1.1 to 3.4 kg active ingredient / ha (1 to 3 founds per acre) in 281 1 (30 gallons) of water, will be a good pre-emergence control of Eohinoohloa cruegalli, BrasBioa kaber, Setaria viridis and Eohinoohloa, colonum received in existing Zurokrohr.

B ice P ie 1 264 * _ \

Aqueous dispersion .

5-methyl-3- (1-piperidiho) -uraoil 13.00? *

Pentachlorophenol 16.00 3 * Hatriun Lignin Sulphonate £ 15.00 ' Hydrated attapulgite 1.75 5t

Water 54.25 f

This preparation is milled down to a fineness in the smallest of every minute of less than 10 microns, whereby “in one constant diapereion is obtained. With a dosage of 33.6 kg of active ingredient / h in 374 1 Waieer (30 pounds / aore), 40 Omllone), this preparation results in a fight against

009826/2033 BAD OR1GIÄ ^{: l:}

2405-9 / 10-0

annual and perennial broad-leaved weeds and Grasuii herbs, such as Agropyron rtpene, 8etaria faberll, Aabrosla artamisiifolia and Ohenopodluo albua, the In firebreak grow in forests "

Example 265 Aqueous concentrate

-J- (hexahydro-1-azepinyl) - 10 6-methyluracil, K-string

Sodium Lauryl Sulphate '1

Water 89

For the preparation of the aqueous concentrate, solder the at * the solid components in water · See Kansentrat läeet see easily grounded on use concentrations and by spraying raise.

These watery concentrates can be comfortably tied with a band * Apply pressure sprayer. With 1.1 to 2.2 kg of active ingredient / k * in 374 liters of water (1 to 2 pounds / acre, 40 gallons) becomes one excellent pre-emergence vaccination of 8etaria, lohinochloa and young sorghum halepenee in beetehendea 2uokerronr. With 45 kg active ingredient / ha in 935 1 water (40 pounds / aore, 100 gallons) you get a fighting variety of clay annual and perennial weeds on industrial land " and railway gravel

006826/2033 .- 59 -

BAD ORIGIN ^ .... ,,

2405-9 / 10-G ™

Example 266

Emulsifiable oil

5 ~ bromo-6-methyl-3- (1-piperidino) -20 »0 + uracil

Alkylaryl polyether alcohol 2.5 Jt

oil-soluble petroleum sulfonate 2.5 t

Isophorone 75.0 ji

For the production of the emulsifiable oils, dororethen Components used to create a homogeneous solution The oil can then be emulsified for use in Waeeer.

This emulsifiable oil is suitable for combating weeds on open-track lines, shunting yards and level lines. If you dilute the agent with 935 1 water / da and apply clay to a rail spraying truck with 11.2 kg active ingredient / ka »a mild vegetation such as Agropyron repene, Digitatia ep. _f Oynooon daotylon, Bromus teotorum, Aabroeia artemielifolia, Xanthlum sp., Chenopodiüm albun and Srigeron oanadensia, long-term control. ^; . .

The emulsion is AUOH very good door the Btuwhbekiapfimg "; if you dilute it with water so that you have 995 1 waeeer 11.2 kg (10 founds in 100 gallons). If one dl · ··· mixture on undesirable oil turbulences, such as Llqüidambtr etyra-

009826/2033

·· 60 -

BATH

2405-9 / 10-G (, ή

ciflua, crab apple, ⁴ oak, maple and poplar, sprayed on, if the foliage is thoroughly moistened, excellent control of the bushes is obtained.

Example 267 Emulsifiable oil suspension

5-3rom-6-methyl-3- (1-pyrrolidiiyl) - 25 t

uracil

Mixture of Poiyalkoholoarbonsäure- 6 ^ ester and oil-soluble petroleum sulfonites

Diesel oil> J. · ■ '· ■ 69 5 ^

The above components are mixed together and ground on a roller, pipe or sand mill until essentially all particles of the active ingredient are less than 10 microns in size. The suspension obtained can be diluted in water or can be further diluted with weed oils in order to Qpritetn them to raise. ·. . -

■■; '■■ ■ -.! ■ · ■ - ■; ·· * ■ #. . ''

If you dilute this preparation old 748 1 uncooked oil (51 (Lion Herbicidal Oil No. 6) and _{apply it with 11.2 pounds 22 9} 4 pounds of active ingredient / ha (80 gallons of oil; 10 pounds 20 pounds / acre) excellent control of weeds, such as Ipo "moea, Stellaris sp., Amaranthue ep", Chenopodium alfcum _s Aebil ~ 'lea millefolium, Ambrosia artemieiifolia ₉ Dauoua oarota _g Agro-

BATH ORIGINAL

: 2405-9 / 10-σ

pyron repens, Panioum capillare and Digitaria ep., and Biohe- and maple saplings received on railway lines

Example 268 Tank mixture

A) Mix as a tank mix 11.2 kg (10 pounds) of 5-bromo-6-methyl-3- (i-piperidino) -uraoil as wettable powder (£ 80) and 2.2 kg (2 pounds) of 4,6-dinitro-p-sec-butylphenol in 37 1 (4-gallona) oil and brings the preparation in one Dosage of 13.5 kg active ingredient / ha in 935.1 water (12 Pounds / acre, 100 gallons) growing along rows of saunas Weeds on. A rapid kill of annual and perennial broad-leaved weeds and Grass weeds with excellent weed control.

B) 16.8 kg (15 pounds) of a water dispersible powder formulation (80% of 5-bromo-3- (hexahydro-1-aeepinyl) -6-raethyluracil and 26.9 kg (24 pounds) of the vatriuasal of 2,2-dichloropropionic acid (85 pounds) are dissolved in 935 liters of water (100 gallons) dispersed and blended.

This agent gives good control of perennial and broadleaf weeds on railroad roads. With a dosage of 935 1 of this preparation / ha (100 OaI-

009826/2033

-62- * 'v-vr \.

BATH ORIGINAL

2405-9 / 10-G

Ions / Acre) will be a good control of Sorghum htlepenee, Cynodon dactylon, Cyperus, Echinochloa crusgalli, Digitaria sp., Plantagο sp., Ambrosia artimisiifolia and Bidene sp. obtain.

C) 21.3 kg (19 pounds) of a water dispersible powder formulation (80 #) of 5-Bromo-6-methyl-3- (1 * -pyrrolidinyl) -uracil and 22.4 kg (20 pounds) of ITa salt of 2,2-diochloropropionic acid (85 #) are in 467 to 935 1 water (50 to 100 gallons) dispersed and mixed. If you spray 1 hectare with the agent obtained, it becomes a good one Fighting annual as well as perennial grasses and broad-leaved weeds along railway lines and grow around loading ramps "

This results in a fight against those that are difficult to kill Weeds such as Digitaria sp ,, Bumex ep., Ambrosia artemisiifolia, Chenopodium album, Amaranthu · ep., Croton Eating, Mollugo verticillata, Bidene biplnnata and sp., Solanum sp., Medioago lupulina, Polygonum avioulare, Plantation sp., Euphorbia maculata and Abutilon theophrasti medio.

E) 13.5 kg of 5-bromo-6-methy1-3- (1-piperidino) uracil in the form of a wettable powder (80 ^c / o) and 39.2 kg of ammonium eulfamate are mixed as a tank mixture in 935 liters of water (12 respectively.

009826/2033

- 63 ORIGINAL BATHROOM

tfyi -;

2405-9 / 10-G £ V

35 pounds; 100 gallons).

This agent is used to treat the infestation of a sprite Power line, used by mixed bushes such as "gum", snowball * willow, cedar, Sich · and maple, until the undesired plants are thoroughly wetted. Good control of these types of undergrowth is obtained.

With a dosage of 52.7 kg active ingredient / ha in 935 liters of water (47 pounds / acre; 100 gallons) annual and combats perennial broad-leaf weeds and grass weeds, a rapid contact effect and extensive weed residue control is obtained weeds controlled belong to Digitaria ep. " Andropogon virginicus, Xanthium ep., Hibiscus trionua and oak, maple and Liquidambar-Styraciflua-Sohöeelinge.

Fixed means

B eie ρ 1 e 1 269 dusts

3- (hexahydro-1-azepjLnyl} -4HBethjl- 'i0 _t 0

uracil

Talk 90

BATH ORIGINAL

2405-9 / 10-G

if

The components are mixed and comminuted £ once ground (hammer mill of the type Micropulverizer) until the Uraoilteilehen to a diameter of about 10 microns, followed by mixing again ₀

Example 270

granules

5-bromo ~ 6-methyl ~ 3- (i-pyrrolidinyl) - 5 # uracil

anhydrous sodium sulfate $ 10>

JWell swelling sub-bentonite tone 85 #

The components are mixed and finely ground »What to moistened with water and granulated. The 'granules are then dried and sighted.

The granulate can be conveniently applied by hand for the "point-wise ¹¹ treatment of unwanted tufted grasses" that grow in agricultural areas · With a dosage of 22.4 kg active ingredient / ha, good control of Muhlenbergia, Dactylis glomerata, Paspalum urvillei and "Kentucky 31 fescue "received * ·

2405-9 / 10-G

Example 1 ,,. 2? 1

Pellets

5 ~ bromo-6- = raethyl-3- (1 -piperidino) - 25 # uracil

anhydrous sodium sulfate 10 f »

Sodium lignin sulfonate 10 #

Ca, Mg «* bentonite 55 #

The components are mixed and finely ground * whereupon they are moistened with 18 to 20 1 ° of water and extruded through nozzle holes. The extrudate is cut into pellets in the shape obtained and dried.

These pellets are suitable for weed control on S «raeeen-Schutagelandern, in the vicinity of bridges, windmills and road signs. They can be easily applied by hand in doses of 11.2 to 23.0 kg of active ingredient / ha. Excellent control of annual and perennial grasses and broad-leaved weeds such as Sorghum halepense, Gynodon dactyl on, Digitaria ap., Agropyron repene , Apocynum, Asolepjaa ap. » Veronica and Ambrosia artemieiifolia.

Q0IÄ26 / 2033 BAD ORIQiNAL

2405-9 / 10-G
Example 272

Soluble powder

5-bromo-6-methyl-3- (4-morpholine p) - 50 ^ uracil.

synthetic fine silica 2 # Sodium Metasilicate, Anhydrous 25 S ^

Potassium chloride 22 % Dioctyl sodium eulfosuccinate 1 %

The components are mixed and converted into a free-flying, non-baking powder finely ground. When aan the powder, in entering a spray tank «the active ingredient dissolves, whereby only the silica remains in suspension.

B e i s P i e 1 273

Edible powder

5-rBron-3- (hexahydro-1 ~ a.zepinyl) - 80.0? 6 6-methyluracil

Sodium Lauryl Sulphate 0.6 f Sodium Lignin Sulfonate $ 2.0 Kaolin clay. 17.4 Jt

The components are welded and then finely grinded essentially the geaaattn solids · «int part size

BAD ORIQtHAU

2405-9 / 10-G

below 50 microns · Dae Gemieoh will then trntut to eur Mixed homogeneity,

The netetoare powder is used as an AllEwtok weed killer on industrial bars and railroad gravel. With 16.8 to 28.0 kg of active ingredient / ha In 995 1 tfa ·· «? becomes tin · excellent control of Brigtron oanadensie, Oenothera, phytolaooa amerioana, Chrysanthemum leuoanthtmum, Xanthium ep. _f Fotentllla anserina, Digitaria ep. and Bragroitie peotinaoea received *

¹ A-. '

-68-009826 / 2033

BATH ORIGINAL

Claims (1)

Claims A N- a cycloimino group with 2 to 14 carbon atoms and a maximum of 5 heteroatoms let, X oxygen or sulfur »
R ₁ hydrogen, chlorine, bromine, "fluorine, J ¹ Od ₉ ifitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 lie 4 Carbon atoms »hydroxymethyl or alkexynetliyl with 2 to 5 carbon atoms »R ₂ alkyl with 1 to 3 carbon atoms and R, hydrogen or alkyl with 1 to 3 carbon atoms with the proviso that R ₁ and R ₂ combine ale (CHg) _n « where η is a whole Number 'same 3 bio 3 is * 2. Means according to claim 1, gekennseiohnet duroh a Sehalt to 5-bromo- »6-methyl-3- (1-piperldino) -uraoil all active ingredients. 009826/2033 3, means according to claim 1 »characterized by a content of 5-chloro-6-methyl-3- (1-piperidino) -uraoll as active ingredients 4. Agent according to claim 1, characterized by a content of 5-bromo-6-methyl-3- (1-pyrrölidinyl) -uraoil as all active ingredients. 5 «Agent according to claim 1, characterized by a content of 5-chloro-6-methyl-3- (1-pyrrolidinyl) -uracil ale active substance, 6. Agent according to claim 1, characterized by a content of 5-bromo-6-methyl-3- (hexahydro ~ 1-azepinyl) uracil as an active ingredient. ^y 7. Means according to claim 1, characterized duroh a content to 5-chloro-6 «methyl-3- (hexahydro-1-azepinyl) -uraoil as Active ingredient. 8. Means according to claim 1, characterized duroh a content to 6-methyl-3- (hexahydro-1-azepinyl) -uraoil as the active ingredient. 9. Medium naoh Claim 1, characterized duroh a salary to 5-bromo-6-methyl-3- {4-morpholino) uracil as active ingredient to «New connection of the formula - 70 - BATH ORIGINAL wherein fs. A N- a cyeloimino group with 2 to 14 carbon atoms and a maximum of 3 heteroatoms », X oxygen or sulfur R _{1 is} hydrogen, chlorine, bromine, fluorine, iodine, nitro, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxymethyl or alkoxymethyl with 2 to 5 carbon atoms,
Alkyl with 1 to 3 carbon atoms is hydrogen or alkyl with 1 to 3 carbon atoms, with the proviso that R ₁ and R ₂ ^ala ( ^CH 2 ^ ri ^{combined can t} * 1η, where η is an integer equal to 3 to 5 11. 5-Bromo-6-methyl-3- (1-piperidino) ~ uraoil. 12. 5-0hlor-6-methyl-3- (1-piperidino) -uracil, 13. 5-Broa «6-methyl-3- (1-pyrrolidinyl) -ura oil * § O SS = I ff 3 = 0 BATH ORIGfNAl. " 2405-9 / 10-G 16. 5-chloro-6-methyl-3- (hexahydro-1-azepinyl) -uraeil. 17 # 6-methyl-3- (hexahydro-1-aze pinyl) -uraeil, 18. 5-Bromo-6-ethyl-3- (4-inorpholino) -uraoil · 009826/2 0 33 BAD ORIQiNAL