Rivas is a depairtment o the Republic o Nicaragua. It covers an aurie o 2,155 km² an haes a population o 166,900 (2005 census). The depairtment's caipital is the ceety o Rivas.
Rivas is kent for its fertile sile an brawnnie beaches. Throughoot the depairtment, thare are mony succar cane, plantain, tobacco, an ither crop plantations. The depairtment borders Loch Nicaragua tae the east an the Paceefic Ocean tae the wast. The soothren pairt o the depairtment borders wi Costa Rica. A sma fishermen veelage, cried San Juan del Sur, haes turned intae a popular tourist attraction acause o the great beaches in the aurie. Anither major tourist attraction is Ometepe, a lairge volcanic island inhabitit bi aboot 32,000 fowk (2005 census).


As weapproach the Fourth of July and enjoy a nice barbecue, rodeo or fireworks -maybe all three, take a moment at some point during the day to remember justwhy we are celebrating.
Wecommemorate those who were willing to put pen to paper and sign their name to adeclaration of independence from what they believed at the time was atyrannical government – England. No small act. In doing so they made themselvesa target of the most powerful country in the world, with a king willing to goto war to force the "colonists" back in line.
We would dowell to remember those brave souls and honor them by making sure our owngovernment does not act in a tyrannical manner to its own people.
Some wouldsay that it's too late, that factions in our government have already conspiredto take away our rights – that they've acted astyrants, trampling on the very ideals that led to our great country. That maybe so, but keep in mind that we still do not bow to a king and under our systemof government there are avenues, far short of war, to kick the tyrants out.
We live ina great country and we have many reasons to be proud of those that led beforeand high hopes for those that will lead in the future. May everyone have a safeand happy Independence Day.


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UPDATE: Police Probably Will Arrest Driver Who Hit Cyclist [PHOTOS]
K2 Radio News
Kevin Koile - Townsquare Media
UPDATE 4:50 Thursday: Casper police probably will arrest the driver of the SUV that hit a cyclist near First Street and North Beech Street on Thursday morning, Lt. Mike Thompson said Thursday afternoon.
But the charges depend on the results of the ongoing investigations and the victim's recovery, Thompson said.
"I would expect there will be something but it's going to be what extent will the charges be, and a lot depends there, again, on how this victim's doing," he said.
The accident occurred just before 7:40 a.m. when the SUV and the cyclist were traveling in opposite directions, Thompson and other police officers said.
The names of the driver and the cyclist, both young males, have not been released, Thompson said.
The collision scattered bicycle parts along First Street, which was closed for several hours. The victim sustained serious injuries and was taken to Denver for treatment at a Level I trauma care hospital.
The magnitude of the accident brought multiple investigators to the scene, Thompson said.
"Our accident investigators, detectives, and members from the district attorney's office (are working) so that we make sure that in the end that when this guy would be arrested it's going to be for the appropriate charges," he said.
Officers executed several search warrants, including the driver's vehicle and another may have been to a place where the driver had been partying the night before, Thompson said.
ORIGINAL STORY: The Casper Police Department is investigating after a motorist collided with a cyclist near the corner of First Street and North Beech Street on Thursday morning.
Sgt. Richard Brown said the accident happened just before 7:40 a.m.
"The person who was on the bicycle has been transported to Wyoming Medical Center for treatment, and they're now on the way to Denver for further treatment – we don't know the status (of that person) right now, and it's still an ongoing investigation," Brown said.
CPD is conducting its investigation between North Durbin Street and North Kimball Street.
Police Lt. Mike Thompson said the vehicle was an SUV, and that investigators are looking at multiple factors in the accident.
"We're still trying to make a determination what vehicle or movements were taking at that time and what condition the traffic signals were," Thompson said.
Brown would not say whether charges are pending against the motorist. We will update this story with additional information once it becomes available.
Anthony Pollreisz, Kevin Koile and Tom Morton have contributed to this story.
Categories: Casper News

redpajama_set_name: RedPajamaCommonCrawl


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Tests of L1 development
Tests of L2 learning
Tests of linguistic research
Tests of cognitive development
Narrative Production Test for German Sign Language
The Narrative Production Test for German Sign Language (NaKom DGS) assesses narrative and morpho-syntactic competences in deaf children 4-11 years old. This test is an adaptation of the British Sign Language Production Test (Narrative Skills) by Herman et al. (2004). The NaKomDGS was developed by Vera Kolbe in cooperation with Claudia Becker in the Department of Sign Language Pedagogy and Audio Pedagogy at Humboldt-Universität zu Berlin, Germany.
NaKom DGS assesses content, structure and correct narrative sequence in children´s DGS narrations as well as use of depicting signs, directional modifications, aspect and manner and constructed action.
The standardization sample consists of narrations of 72 native signing children with access to DGS from birth through Deaf DGS signing parents. 65 children of the standardization sample are Deaf native signers, 7 are hearing CODAs (Children of Deaf Adults). The children in the standardization sample are between 4 to 11 years old.
NaKom DGS is intended for use with children who use DGS as a first language or who are multilingual with DGS and other languages.
NaKom DGS elicits narrations via a short language-free stimulus video. The children narrating the video story in DGS are filmed. The filmed narration is subsequently analyzed using an Excel score sheet. Individual test results of children are compared with the percentiles of the standardization sample. Percentiles are provided for every age. Test administration takes about 15 minutes per child and test evaluation between 30-60 minutes per test.
Figure 1: Example from the tester-friendly score sheet. The scoring criteria for the items are provided in the excel sheet. Here three items from the category aspect are shown.
NaKom DGS is available in the context of a certification course for professionals and scholars at KoRa (Humboldt-Universität zu Berlin): https://kora-berlin.de
Results of the adaptation study and information about the test in DGS, German, English and International Sign can be found here: https://nakom.hu-berlin.de/
The test instrument was controlled for the following psychometric properties: validity, reliability, practicability as well as child appropriateness.
NaKom DGS achieved good results in all psychometric measures:
Internal consistency
- Cronbach´s α (n = 72): narration 0.94, grammar 0.88
Interrater-reliability
- Cohen´s κ (n = 21): narration 0.71, grammar 0.68; Many-Facet-Rasch-Measurement: very good consistency in rater severity
Intrarater-reliability
- Cohen´s κ (n = 10): narration 0.79, grammar 0.86
NaKom DGS provides information about the development of children´s competences according to age in all categories tested. For all categories a statistically significant effect of age is estimated by a General-Additive-Model regression.
One of the strengths of NaKom DGS is the assessment of sign language production, and not reception, thus it is not limited by variations in DGS. There is no language used in the stimulus video. The testers sign the test administration explanations and questions personally, therefore the DGS can be adapted to the variation familiar to the evaluated children.
A weakness lies in the complexity of evaluating a signed narration. Testers need to learn how to assess the produced children´s narrations in a certification course.
Summarized by Vera Kolbe (2023).
For further information about NaKomDGS, please contact Vera Kolbe or Claudia Becker at Humboldt-Universität zu Berlin.
Enns, C., Kolbe, V., & Becker, C. (2021). Challenges and solutions in test adaptation: Comparing international experiences with the British Sign Language Production Test (Narrative Skills). Sign Language & Linguistics, 24(2) https://doi.org/10.1075/sll.20010.enn
Enns, C., Kolbe, V. & Becker, C. (2022). Testadaptionen und ihre Herausforderungen - ein internationaler Vergleich von Lösungsansätzen bei der Adaption des British Sign Language Production Test (Narrative Skills). Das Zeichen, 119.
Herman, R., Grove, N., Holmes, S., Morgan, G., Sutherland, H. & Woll, B. (2004). Assessing British Sign Language Development: BSL Production Test (Narrative Skills). London: City University.
Kolbe, V. (in print). Sprachproduktionstest zu narrativen Kompetenzen in Deutscher Gebärdensprache - eine Testadaption (NaKom-DGS). Berlin: Humboldt-Universität zu Berlin.
Kolbe, V. (2021). Videolecture: Sprachproduktionstest Narrative Kompetenzen in Deutscher Gebärdensprache - ein neues Testverfahren für Kinder (4-11 Jahre).
Kolbe, V. & Becker, C. (2023). NaKom DGS - Sprachproduktionstest zu narrativen Kompetenzen in Deutscher Gebärdensprache. Berlin: Humboldt-Universität zu Berlin.


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La spongada è una focaccia dolce, preparazione tradizionale della cucina della Valcamonica, dall'aspetto di una piccola pagnotta cosparsa di zucchero. Prodotto da forno tipico del periodo pasquale, la spongada viene preparata e consumata anche in altri periodi dell'anno.

Preparazione e ingredienti
La preparazione del dolce segue una ricetta che può presentare variazioni nelle proporzioni degli ingredienti a seconda delle tradizioni dei singoli borghi camuni. Di base, la ricetta prevede il mescolamento di due diversi impasti in due momenti successivi.

Il primo impasto è a base di farina bianca, zucchero, burro, uova, lievito, con aggiunta dell'aroma di vaniglia . Dopo circa tre ore di lievitazione, alla massa così lievitata si aggiunge un secondo impasto a base di farina, zucchero, burro o strutto, uova intere, tuorli d'uovo, vanillina, lievito di birra. Dopo l'amalgama, il nuovo impasto viene sottoposto a una seconda lievitazione per qualche ora, prima di essere modellato in forme di palle o pagnotte di circa 150 grammi.

Le pagnotte vengono poste a lievitare ancora per il tempo necessario a ottenere un raddoppio del volume originario.

La cottura delle pagnotte avviene con un passaggio in forno della durata di 20-25 minuti, alla temperatura di 180 °C.

Al momento della presentazione, la spongada viene ricoperta in superficie di zucchero.

Il termine spongada compare già nel vocabolario Bresciano-Italiano del Melchiori del 1817, viene definita: "Focaccia, schiacciata, berlingotto. Pasta nota".

Note

Bibliografia

  Spongada camuna - Distretto Culturale di Valle Camonica

Voci correlate

 Spongarda
 Spongata

Focacce dolci
Dolci pasquali
Cucina della Val Camonica

redpajama_set_name: RedPajamaWikipedia


Authorized Employer contacts without direct access, please submit new hire information using this form or to your account manager directly using a paper new hire form. You can upload paper new hire & direct deposit forms to us via this secure upload page. All submissions will be re-verified by your account managers to insure they were approved by an authorized employer contact.
Hiring with HUB Employee HR Portal: If you are an admin user of the HUB Employee Portal; you can send your newly hired employees their initial paperwork to complete using the HUB "new hire" feature. The HUB new hire feature will guide you & your employee through a secure & paperless process in order to set your employee up with ASAP. Please contact your account manager if the new hire feature is not enabled on your HUB account. If your company isn't using HUB yet at all, please complete this form to activate the app for your company.
1. Complete a W4 - Employee's Withholding Allowance Certificate.
2. Complete Section 1 of the I-9 Employment Eligibility Verification.
3. Present to their employer or hiring manager personal documents as explained on page 9 of the I-9 Employment Eligibility Verification.
5. Be provided an ACA Health Coverage Notice unique to their employer's coverage options.
1. Complete Section 2 of the I-9 Employment Eligibility Verification.
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Share your artwork to learn how others see your work or share your comments to help other artists. Artwork not required. Please join us. FCArts CriTique is a supportive and friendly monthly FCA event that asks questions and makes suggestions if you are stuck on an artwork or looking for general reaction and suggestions to improve your work.
Brian Legan instructs on developing and building acrylic artwork known as "Process Painting" see www.FallsChurchArts.org/classes for more information and detail.


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Donald Duck figurine
Figurines of Disney characters have been manufactured since the early 1930s. Early figurines are usually of Mickey and Minnie Mouse an, a little late, Donald Duck. Many of these have been of poor quality but the ceramic figures from two periods are of particular interest to collectors.
In the late 1950s, Disney licensed a variety of miniature ceramic figurines of its cartoon characters. These were manufactured between about 1955 and 1960 by Hagen-Renaker. The first figures were from Disney's then current Lady and the Tramp. These were followed by figures of characters from the Alice in Wonderland, Dumbo, Bambi and Cinderella movies and cartoon characters, including Mickey Mouse, Donald Duck, Goofy, Pluto and Huey, Dewey and Louie. Some of these were later re-issued and a set of Fantasia figurines was produced in 1982.
In 1992, Walt Disney Studios began producing fine animation art figurines itself. These are made from a special low-fire porcelain, often enhanced with another material such as crystal, glass or a precious metal. Each figurine has a back stamp with Walt Disney's signature and a symbol indicating the year in which it was made.
Disney figurines available now
DISNEY BRITTO SIMBA MINI FIGURINE
DISNEY BRITTO JIMINY CRICKET MINI FIGURINE
DISNEY BRITTO MICKEY MOUSE WITH HEART MINI FIGURINE
DISNEY BRITTO TINKER BELL KISSING MINI FIGURINE
DISNEY BRITTO MINNIE MOUSE FIGURINE - LARGE


A sleeping child.... - Snuggled Up, Inc. PO Box 341384, Dayton, OH 45434 www.snuggledupinc@gmail.com FacebookTwitter Snuggled Up Inc.
My sweet girl was beyond tired. She is fortunate to have a bed, however tonight she fell asleep before dinner in her bean bag. As I watched her sleep I was reminded how many children may not have a bed and that a couch or bean bag may be their 'bed,' this is why Snuggled Up started...to help children have a bed and bedding of their own.
"Always kiss your children goodnight, even if they're already asleep."


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La estrella de Campbell (HD 184738 / HIP 96295 / BD+30 3639) —también conocida como la estrella de hidrógeno de Campbell— es la estrella central de la nebulosa planetaria PK 064+05 1.
Se localiza en la constelación del Cisne 2,5º al norte de Albireo (β Cygni) y 1º al este de φ Cygni.
Se encuentra a unos 1200 pársecs —3900 años luz— del sistema solar.

De magnitud aparente +10,41, la estrella de Campbell es una estrella de Wolf-Rayet de carbono de tipo espectral [WC9]. Extraordinariamente caliente —tiene una temperatura efectiva de 55 000 K—, es 6000 veces más luminosa que el Sol.
Es una estrella deficiente en hidrógeno en un avanzado estado evolutivo.
Aunque su masa actual es un 60 % de la que tiene el Sol, se piensa que su progenitora era una estrella de ~ 2 masas solares ahora en la fase de la rama asintótica gigante (RAG); en última instancia se transformará en una enana blanca.
Su composición química es muy diferente a la del Sol; es deficiente en hierro (Fe/O ~ 0,3) pero muestra unos elevados contenidos de carbono y neón (C/O ~ 30).

La nebulosa planetaria asociada a la estrella de Campbell tiene una edad aproximada de 700 u 800 años.
En contraste con el polvo asociado a otras estrellas WC tardías, compuesto fundamentalmente por carbono amorfo, esta nebulosa planetaria muestra polvo de silicato cristalino, indicando un cambio reciente de una química dominada por el oxígeno a otra dominada por el carbono.
Se ha propuesto que la existencia de una compañera estelar podría compaginar la composición del polvo de la nebulosa planetaria con la deficiencia de hidrógeno de la estrella central.

Referencias

Estrellas de Wolf-Rayet
Estrellas variables
Nebulosas planetarias
Constelación de Cygnus


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What to Do With the Digital Remains of a Failed Relationship
After the split, you're left with an abandoned attic's worth of stuff: on your phone and hard drive, in your inbox. It's stuff that used to matter, and still does. It's stuff that hurts. It's stuff you loved. What do you do with it?
It's impossible to plow through a committed relationship in an industrialized nation without piling up an abundant digital record. You'll have chat transcripts, tagged photos on Facebook, beautiful photos from a DSLR, email letters, Skype call screenshots, texts—so, so many texts. Your first instinct will be to throw it all away.
That's not a reflex to be ashamed of—just like you wouldn't want to stare at a framed photo of your ex while you're hurting, you don't want to look at hundreds of messages and JPEGs detailing that person either. We're all hypersensitive when it happens, and we're living in an age of hyper-info. There are more grains of salt to catch in your heart wound than ever before. This isn't easy—but let's try.
Wait a month. Wait longer. Wait until you can look at his or her Facebook profile without feeling something bad in your chest, or the urge to throw your laptop. No good decision, in this century or any other, has ever been made in the fresh wake of a breakup. Please, please don't throw your laptop.
Don't delete these. Really, don't. You'll regret it if you do. Not because maybe someday you'll get back together and be so glad you kept it all. You probably won't. But these pictures aren't just small monuments to a failed romance, they're high-resolution instants from your life, recorded forever, unfading. It's not just your ex's smile that you miss and wish you could have back and oh god I need a drink—it's the way you were at a particular moment a shutter snapped and a digital sensor touched light. It's your dog, your apartment, your haircut, your vacation, your job, your old bike—everything that was you for that moment, regardless of who you were dating and who you loved. This is matter you'll want years and decades from now—don't be rash and trash it.
Instead, vault it. Copy everything that's too much to look at onto an external hard drive or some remote backup system, and then delete it from your machine. Put that hard drive in a sock drawer or under your bed. Give it to a friend. Place it where it won't distract and won't harm, but, when you're ready, can provide a vivid reminder of who you used to be. That's incredibly powerful! Don't destroy it on a whim.
Yeah, toss these. All leftover playlists will do is smear heartbreaking meaning and nostalgia over songs you'd otherwise enjoy. Remember, you made this playlist explicitly for your ex—you tailored songs you both love in an order you thought might make them smile, miss you, have sex with you. And all those memories could swamp you based on nothing but this otherwise innocuous list of MP3s. So get rid of the list. Keep the songs though.
Burned CDs
If you got a burned playlist in return, again, toss. It's an artifact that carries all the hurtful weight of a physical object with none of the sentimentality. Do you even have an optical drive anymore?
Emails can be as banal and brief as any text message, but there are plenty of exceptions: long ones penned while abroad, or traveling, mail with attachments, breakup letters, I Miss You letters. Rather than sift through everything, archive it all. Do a search for his or her email, select all, and pack it away into a folder or some other deep depth of your account. Remember: this email is part of your life history. It includes details you won't remember by the time you're long over the breakup, and you'll be grateful for them.
Delete—this is just an invitation to wallow and/or leap back into ill-advised contact. Both are bad for you.
Facebook tags
Again, an opportunity to wallow, a web browser shortcut to melancholy. And who wants a future prospect to see a bunch of pictures with your ex?
There should be a pattern emerging here. It's difficult, but you need to discern what baggage is going to be useful even after all the heavy, horrible, hurtful emotions wear off. What are the bytes that'll have significance on their own, without the love connection? What stuff will remind you about your life in some broader sense than a relationship that occupied some months or years of it? What'll be that GIF or TXT you wish to hell you hadn't erased, because who knows what it might've reminded you of about the way you used to be?
Those things deserve backup. The rest was just noise all along.
User Manual is Gizmodo's guide to etiquette. It appears as if by magic every Friday.
Kyle Wagner
What about chat logs!?


While some styles of music go in and out of fashion, fashion hasn't been especially kind to classical music. No thanks to that pesky nine-letter adjective, which carries more stigma than "polka" or "folk," the genre is generally perceived as something that falls outside the scope of so-called normal music; an uptight elitist pursuit that calls to mind gray hair, cummerbunds and loads of disposable income.
Given the average ticket prices to many classical concerts, there's some truth to the latter. And as disposable income has shrunk since the start of the economic crisis in 2007, symphonies have witnessed a concomitant downward trend in ticket sales. Which means the challenge faced by outfits like the Spokane Symphony is now twofold: part perception, part economics.
The symphony has been adapting to the times by plunging into social media. It now boasts 2,656 Facebook fans and around the same number of Twitter followers. One year ago, it debuted a short Casual Classics concert series that turned social media into a creative exercise. The symphony asked audiences to envision Facebook pages for Beethoven, Mozart and Schubert by playing pieces from the composers' friends and contemporaries.
Fun ideas like the Facebook-themed concerts emerged from the organization's rather dry-sounding Revenue Generation Innovation Task Force.
The Casual Classics concert series clearly had youth appeal, but organizers wanted to reach an even broader demographic. So they developed Symphony with a Splash series, which Nienhouse describes as a "happy-hour-type format" that gives people a convenient way to end their working week with a one-hour concert in the early evening.
For the past three years the symphony has also been partnering with Arbor Crest Wine Cellars to hold Soirees on the Edge, another concert series that offers a relaxed alternative to indoor events by featuring "more cutting-edge music" written by contemporary composers.
"What's fun about that series is that the setting is just so beautiful. In the evening as the concert is going on, the sun sets over the city and the lights of the city come on," says Nienhouse. The Soirees on the Edge are deliberately aimed at a different crowd that the one that will likely attend Video Games Live, a visual spectacular that, as the name suggests, will highlight music from popular video games.
But social media outreach and diverse content only address perception. When it comes to economics, the Spokane Symphony has created initiatives like the Club Maestro program. It gives 21- to 36-year-olds the chance to pay just $15 for quality seats at select concerts.
All these measures seem to be having the desired effect. In 2012, the total number of Spokane Symphony concertgoers increased by 4,450 — a 13 percent year-on-year increase at a time when full economic recovery is still a ways off. It will take a few years to determine how much novelty is necessary to sustain that sort of growth, but any increase at all shows that the symphony has been able to rise to the challenge.


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North Texas man accused of striking another vehicle amidst possible love triangle
Patrick Johnston
A Burkburnett man reportedly used his work truck to strike another man's vehicle around 4 a.m. Tuesday after showing up to the man's residence.
Christopher Shawn Gray, 24, is charged with aggravated assault and possession of a controlled substance.
The victim claimed that Gray was possibly having a relationship with the victim's girlfriend before the alleged incident.
Gray remained behind bars in the Wichita County Jail Wednesday afternoon in lieu of $18,000 total bail on the felony offenses.
According to probable cause affidavits:
Around 4:13 a.m., Wichita County Sheriff's deputies were dispatched to Goodman Road near Kincall Road in Wichita Falls.
Dispatch advised the two parties were separated and the suspect was sitting in a white truck with wording on it. They also told deputies the suspect's name was "Chris."
Upon arrival, deputies found a truck matching the description given stopped in the roadway on Kincall.
A person standing next to the truck identified himself as Gray and said he was the driver of the truck.
The truck had a flat front tire on the passenger side and damage on the front end.
Gray told the deputies he was trying to go the back way into Burkbrurnett, then admitted he was trying to have romantic relations with a woman.
He denied knowing anyone who lived on Kincall Road and said he wasn't going to an address on the road.
Gray also claimed he wasn't in an argument or fight with anyone prior to the deputy arriving. He said he didn't know what the deputy was talking about.
Other deputies arrived on scene and spoke with the reporting party, a man who lives on Kincall Road.
The man confirmed to the deputies that Gray was the one who assaulted him.
He alleged that Gray used his truck to strike the driver side of the man's vehicle while he was driving east on Kincall Road.
The man's vehicle had damage on the driver's side consistent with his account of what happened.
The man said he was very scared and afraid Gray would continue to hurt him after Gray struck his vehicle, so he called 911.
He told the deputies he was not injured and didn't need any medical attention.
The man claimed the argument started over the man's girlfriend, whom Gray may be having a relationship with.
In the man's written statement, he claimed he woke up around 4 a.m. to get ready for work. He wrote he was approached by Gray asking if he had a call for service by a tire service company.
The tire service company's name was also listed on the truck Gray was driving.
The man stated he didn't have an explanation for why Gray was at his residence.
He reportedly told Gray he would have to call and find out if he had a call for service, because he did not know.
The man stated he then left in his vehicle and that Gray followed him in the truck.
He also said Gray got out of his truck after striking the man's vehicle and asked the man what he took from him. Gray continued yelling at the man, he claimed.
Gray was read his Miranda warning and placed into custody for the second-degree felony assault. He refused to speak to deputies about the incident.
The deputy summoned a wrecker to impound Gray's truck. While taking an inventory of the truck's contents, the deputy found a small clear plastic baggie int eh driver side door storage compartment.
The baggie contained a clear crystal-like substance that field tested positive for methamphetamine. The substance weighed 1.2 grams.
Gray was then charged with possession of a controlled substance in penalty group one weighing more than one gram but less than four grams – a third-degree felony.


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Sylvester James "Jim" Gates, Jr
Massachusetts Institute of Technology, B.S. in Mathematics
Massachusetts Institute of Technology, B.S. in Physics
Massachusetts Institute of Technology, Ph.D. in Physics
Sylvester James "Jim" Gates, Jr., (born December 15, 1950) is an American theoretical physicist. He received two B.S. degrees and a Ph.D. degree from the Massachusetts Institute of Technology, the latter in 1977. His doctoral thesis was the first one at MIT to deal with supersymmetry. In 2017, Gates retired from the University of Maryland, and is currently the Brown Theoretical Physics Center Director, Ford Foundation Professor of Physics, an Affiliate Mathematics Professor, and a Faculty Fellow, Watson Institute for International Studies & Public Affairs at Brown University. While at the University of Maryland, College Park, Gates was a University System Regents Professor, the John S. Toll Professor of Physics, the Director of the String and Particle Theory Center, and Affiliate Professor of Mathematics. Gates served on the U.S. President's Council of Advisors on Science and Technology, contemporaneously on the Maryland State Board of Education from 2009-2016, and the National Commission on Forensic Science from 2013-2016. He is known for his work on supersymmetry, supergravity, and superstring theory. In 1984, working with M.T. Grisaru, M. Rocek, W. Siegel, Gates co-authored Superspace, the first comprehensive book on the topic of supersymmetry. In 2017, working with Frank Blitzer and Stephen Jacob Sekula, he co-authored Reality in the Shadows (Or) What the Heck's the Higgs? In 2019, together with Cathie Pelletier, he co-authored Proving Einstein Right: The Daring Expeditions that Changed How We Look at the Universe.
In 2006, he completed a DVD series titled Superstring Theory: The DNA of Reality for The Teaching Company composed of 24 half-hour lectures to make the complexities of unification theory comprehensible to non-physicists. In 2012, he was named a University System of Maryland Regents Professor, only the sixth person so recognized in the system's history. He is a past president of the National Society of Black Physicists, and is a NSBP Fellow, as well as a Fellow of the American Physical Society, the American Association for the Advancement of Science, and the Institute of Physics in the U.K. In 2019 he was elected to the presidential line of
the APS where he is currently serving as President-Elect. He also is an elected member of the American Academy of Arts and Sciences, and the American Philosophical Society. In 2013, he was elected to the National Academy of Sciences, becoming the first African-American
theoretical physicist so recognized in its 150-year history. On November 16, 2013, Prof. Gates was awarded the Mendel Medal by Villanova University "in recognition of his influential work in
supersymmetry, supergravity and string theory, as well as his advocacy for science and science education in the United States and abroad." President Obama awarded Prof. Gates the 2011 National Medal of Science, the highest award given to scientists in the U.S., at a White House ceremony in 2013. During 2014, he was named the Harvard Foundation's "Scientist of the Year." In 2018, he was elected to serve in the presidential line as Vice President of the American
Physical Society, moving to President Elect in 2020. In 2019, he was invited to serve on the American Bar Assoc Steering Committee for the Annual Prescription For Criminal Justice And Forensic Science. In 2020, he will begin serving on the Board of Trustees of the Mathematical Sciences Research Institute.
He continues to broadly engage video documentaries with appearances or cameos.
He currently continues his research in supersymmetry in systems of particles, fields, and strings.
EXPLORE THE EXPERT CONNECT COMMUNITY!
George Carruthers
George M. Low
M. George Craford


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Justia Patents At 2-position And At 4- Or 6-positionUS Patent for Substituted phenyluracils Patent (Patent # 6,455,697)
Substituted phenyluracils
Jan 16, 2001 - Bayer Aktiengesellschaft
The invention relates to novel substituted phenyluracils of the general formula (I) in which R1, R2, R3, R4, R5 and R6 are each as defined in the description, to processes for their preparation, to novel intermediates and to their use as herbicides.
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This application is a divisional application of U.S. application Ser. No. 08/983,631, filed Jan. 23, 1998.
The invention relates to novel substituted phenyluracils, to processes for their preparation, to novel intermediates and to their use as herbicides.
It is known that certain substituted uracils have herbicidal properties (cf. EP 408382/U.S. Pat. No. 5,084,084/U.S. Pat. No. 5,127,935/U.S. Pat. No. 5,154,755, EP 5,63,384, EP 648749, WO 91/00278, U.S. Pat. No. 4,979,982, U.S. Pat. No. 5,169,430, DE 4329537). However, these compounds have hitherto not attained any major importance.
This invention, accordingly, provides the novel substituted phenyluracils of the general formula (I)
in which
R1 represents hydrogen, halogen or optionally substituted alkyl,
R2 represents optionally substituted alkyl,
R3 represents hydrogen, amino or respectively optionally substituted alkyl, alkenyl or alkinyl,
R4 represents hydrogen, cyano or halogen,
R5 represents cyano or thiocarbamoyl, and
R6 represents one of the groupings below
—C(R7,R8)—C(R7,R8)—R9 or —C(R7)═C(R8)—R9
R7 and R8 are identical or different and each represents independently of the other hydrogen, hydroxyl, mercapto, halogen or respectively optionally substituted alkyl, alkoxy or alkylthio, and
R9 represents cyano, formyl, alkylcarbonyl, the grouping —CO—OR10 or the grouping —CO—N(R11,R12), where
R10 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl and heterocyclylalkyl,
R11 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkoxy, alkenyl and alkinyl, and
R12 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl and heterocyclylalkyl, or together with R11 represents alkanediyl.
The novel substituted phenyluracils of the general formula (I) are obtained when
(a) aminophenyluracils of the general formula (II)
R1, R2, R3, R4 and R5 are each as defined above,
or acid adducts of compounds of the formula (II)
are reacted with an alkali metal nitrite or alkyl nitrite and with a hydrogen halide (HX1) or a metal halide (MX1), if appropriate in the presence of a diluent, and the resulting diazonium salts of the general formula (III)
R1, R2, R3, R4 and R5 are each as defined above and
X1 represents halogen,
are reacted with acrylic acid derivatives of the general formula (IV)
C(R7R8)═C(R7)—R9 (IV)
R7, R8 and R9 are each as defined above,
in the presence of hydrogen halides (HX1), if appropriate in the presence of catalysts, if appropriate in the presence of water and if appropriate in the presence of the organic solvent employed initially, or
(b) substituted phenyluracils of the general formula (Ia)
R1, R2, R3, R4, R5, R7, R8 and R9 are each as defined above,
but where at least one of the radicals R7/R8 represents hydrogen and at least one further radical R7/R8 in a position vicinal to the first represents halogen
are reacted with an acid acceptor, if appropriate in the presence of a diluent.
It is also possible to convert the compounds of the general formula (I) into other compounds of the general formula (I) according to the above definition using other conventional methods, for example by amination or alkylation (e.g. R3: H→NH2, H→CH3), reaction with hydrogen sulphide (e.g. R5: CN→CSNH2), nucleophilic substitution (e.g. R8: Cl→SCH3), if appropriate addition of hydrogen, halogen or hydrogen halide to a C—C double bond (cf. definition of R6), hydrolysis (e.g. R9: CN→COOH).
If the compounds of the formula (I) according to the invention contain olefinic double bonds (cf. definition of R6), the invention relates both to the individual E and Z or cis and trans isomers separable by conventional methods, and also to any mixtures of these isomers.
The novel substituted phenyluracils of the general formula (I) have strong herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which
R1 represents hydrogen, fluorine, chlorine, bromine or optionally fluorine- and/or chlorine-substituted C1-C4-alkyl,
R2 represents optionally fluorine- and/or chlorine-substituted C1-C4-alkyl,
R3 represents hydrogen, amino, represents optionally cyano-, fluorine-, chlorine- or C1-C4-alkoxy-substituted C1-C6-alkyl or represents optionally fluorine- and/or chlorine-substituted C2-C6-alkenyl or C2-C6-alkinyl,
R4 represents hydrogen, cyano, fluorine or chlorine,
R7 and R8 are identical or different and each represents independently of the other hydrogen, hydroxyl, mercapto, fluorine, chlorine, bromine or respectively optionally cyano-, fluorine-, chlorine- or C1-C4-alkoxy-substituted C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkylthio, and
R9 represents cyano, formyl, C1-C4-alkyl-carbonyl, the grouping —CO—OR10 or the grouping —CO—N(R11,R12), where
R10 represents hydrogen or represents optionally cyano-, fluorine-, chlorine- or C1-C4-alkoxy-substituted C1-C10-alkyl,
R10 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted C3-C10-alkenyl or C3-C10-alkinyl,
R10 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, C1-C4-alkyl- or C1-C4-alkoxy-carbonyl-substituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-C1-C4-alkyl,
R10 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio- or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl- C1-C4-alkyl, furyl, furylmethyl, tetrahydrofuryl, tetrahydrofurylmethyl, thienyl, thienylmethyl, tetrahydrothienyl, tetrahydrothienylmethyl, perhydropyranyl, perhydropyranylmethyl, oxazolyl, oxaazolylmethyl, thiazolyl, thiazolylmethyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, dioxolanyl, dioxolanylmethyl, pyridinyl, pyridinylmethyl, pyrimidinyl or pyrimidinylmethyl,
R11 represents hydrogen or represents respectively optionally cyano-, fluorine-, chlorine- or C1-C4-alkoxy-substituted C1-C6-alkyl or C1-C6-alkoxy,
R11 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted C3-C6-alkenyl or C3-C6-alkinyl, and
R12 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio- or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, furyl, furylmethyl, tetrahydrofuryl, tetrahydrofurylmethyl, thienyl, thienylmethyl, tetrahydrothienyl, tetrahydrothienylmethyl, perhydropyranyl, perhydropyranylmethyl, oxazolyl, oxadiazolylmethyl, thiazolyl, thiazolylmethyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, dioxolanyl, dioxolanylmethyl, pyridinyl, pyridinylmethyl, pyrimidinyl or pyrimidinylmethyl or together with R11 represents C2-C6-alkanediyl.
The invention in particular provides compounds of the formula (I) in which
R1 represents hydrogen, fluorine, chlorine, bromine or optionally fluorine- and/or chlorine-substituted methyl or ethyl,
R2 represents optionally fluorine- and/or chlorine-substituted methyl or ethyl,
R3 represents hydrogen, amino, represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents optionally fluorine- and/or chlorine-substituted propenyl, butenyl, propinyl or butinyl,
R4 represents hydrogen, fluorine or chlorine,
R7 and R8 are identical or different and each represents independently of the other hydrogen, fluorine, chlorine, bromine or respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio, and
R9 represents cyano, the grouping —CO—OR10 or the grouping —CO—N(R11,R12), where
R10 represents hydrogen or represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl,
R10 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, pentenyl, propinyl, butinyl or pentinyl,
R10 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
R10 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethyl-, methoxycarbonylor ethoxycarbonyl-substituted phenyl, phenylmethyl, phenylethyl, furyl, furylmethyl, tetrahydrofuryl, tetrahydrofurylmethyl, thienyl, thienylmethyl, tetrahydrothienyl, tetrahydrothienylmethyl, perhydropyranyl, perhydropyranylmethyl, oxazolyl, oxazolylmethyl, thiazolyl, thiazolylmethyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, dioxolanyl, dioxolanylmethyl, pyridinyl, pyridinylmethyl, pyrimidinyl or pyrimidinylmethyl,
R11 represents hydrogen or represents respectively optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, methoxy or ethoxy,
R11 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl or propinyl, and
R12 represents hydrogen or represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i- propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl,
R12 furthermore represents respectively optionally fluorine-, chlorine- or bromine-substituted propenyl, butenyl, pentenyl, propinyl, butinyl or pentinyl, represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl- substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclo-butylmethyl, cyclopentylmethyl or cyclohexylmethyl,
R12 furthermore represents respectively optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethylthio-, methoxycarbonyl- or ethoxycarbonyl-substituted phenyl, phenylmethyl, phenylethyl, furyl, furylmethyl, tetrahydrofuryl, tetrahydrofurylmethyl, thienyl, thienylmethyl, tetrahydrothienyl, tetrahydrothienylmethyl, perhydro-pyranyl, perhydropyranylmethyl, oxazolyl, oxazolylmethyl, thiazolyl, thiazolylmethyl, oxadiazolyl, oxadiazolylmethyl, thiadiazolyl, thiadiazolylmethyl, dioxolanyl, dioxolanylmethyl, pyridinyl, pyridinylmethyl, pyrimidinyl or pyrimidinylmethyl.
The general or preferred radical definitions listed above are valid both for the end products of the formula (I) and, in a corresponding manner, also for the starting materials or intermediates which are required in each case for the preparation. These radical definitions can be combined with each other at will, i.e. combinations between the given preferred ranges are also possible.
Examples of the compounds of the formula (I) according to the invention are listed in the groups below.
R6 has in this case for example the meanings given in the list below:
2-cyano-ethenyl, 2-cyano-1-methyl-ethenyl, 2-cyano-1-chloro-ethenyl, 2-cyano-2-chloro-ethenyl, 2-cyano-1-bromo-ethenyl, 2-cyano-2-bromo-ethenyl, 2-cyano-propenyl, 2-cyano-ethyl, 2-cyano-2-fluoro-ethyl, 2-cyano-2-chloro-ethyl, 2-cyano-2-bromo-ethyl, 2-cyano-1,2-dichloro-ethyl, 2-cyano-1,2-dibromo-ethyl, 2-cyano-2,2-dichloro-ethyl, 2-cyano-2-chloro-1-methyl-ethyl, 2-cyano-2-chloro-1,2-dimethyl-ethyl, 2-cyano-2-chloro-propyl, 2-carboxy-ethenyl, 2-carboxy-1-methyl-ethenyl, 2-carboxy-1-chloro-ethenyl, 2-carboxy-2-chloro-ethenyl,-2-carboxy-1-bromo-ethenyl, 2-carboxy-2-bromo-ethenyl, 2-carboxy-propenyl, 2-carboxy-ethyl, 2-carboxy-2-fluoro-ethyl, 2-carboxy-2-chloro-ethyl, 2-carboxy-2-bromo-ethyl, 2-carboxy-1,2-dichloro-ethyl, 2-carboxy-1,2-dibromo-ethyl, 2-carboxy-2,2-dichloro-ethyl, 2-carboxy-2-chloro-1-methyl-ethyl, 2-carboxy-2-chloro-1,2-dimethyl-ethyl, 2-carboxy-2-chloro-propyl, 2-methoxycarbonyl-ethenyl, 2-methoxycarbonyl-1-methyl-ethenyl, 2-methoxycarbonyl-1-chloro-ethenyl, 2-methoxycarbonyl-2-chloro-ethenyl, 2-methoxycarbonyl-1-bromo-ethenyl, 2-methoxycarbonyl-2-bromo-ethenyl, 2-methoxycarbonyl-propenyl, 2-methoxycarbonyl-ethyl, 2-methoxycarbonyl-2-fluoro-ethyl, 2-methoxycarbonyl-2-chloro-ethyl, 2-methoxycarbonyl-2-bromo-ethyl, 2-methoxycarbonyl-1,2-dichloro-ethyl, 2-methoxycarbonyl-1,2-dibromo-ethyl, 2-methoxycarbonyl-2,2-dichloro-ethyl, 2-methoxycarbonyl-2-chloro-1-methyl-ethyl, 2-methoxycarbonyl-2-chloro-1,2-dimethyl-ethyl, 2-methoxycarbonyl-2-chloro-propyl, 2-ethoxycarbonyl-ethenyl, 2-ethoxycarbonyl-1-methyl-ethenyl, 2-ethoxycarbonyl-1-chloro-ethenyl, 2-ethoxycarbonyl-2-chloro-ethenyl, 2-ethoxycarbonyl-1-bromo-ethenyl, 2-ethoxycarbonyl-2-bromo-ethenyl, 2-ethoxycarbonyl-propenyl, 2-ethoxycarbonyl-ethyl, 2-ethoxycarbonyl-2-fluoro-ethyl, 2-ethoxycarbonyl-2-chloroethyl, 2-ethoxycarbonyl-2-bromo-ethyl, 2-ethoxycarbonyl-1,2-dichloro-ethyl, 2-ethoxycarbonyl-1,2-dibromo-ethyl, 2-ethoxycarbonyl-2,2-dichloro-ethyl, 2-ethoxycarbonyl-2-chloro-1-methyl-ethyl, 2-ethoxycarbonyl-2-chloro-1,2-di methyl-ethyl, 2-ethoxycarbonyl-2-chloro-propyl.
R6 has in this case for example the meanings listed above in Group 1.
Using, for example, 1-(5-amino-4-cyano-2-fluoro-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, sodium nitrite and hydrochloric acid and then methyl acrylate as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme:
Using, for example, 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3,5-dimethyl-4-trifluoromethyl-1(2H)-pyrimidine as starting material and triethylamine as acid acceptor, the course of the reaction in the process (b) according to the invention can be illustrated by the following scheme:
The formula (II) provides a general definition of the aminophenyluracils to be used as starting materials in the process (a) according to the invention for preparing the compounds of the formula (I). In the formula (II), R1, R2, R3, R4 and R5 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2, R3, R4 and R5.
The starting materials of the formula (II) are known and/or can be prepared by processes known per se (cf. EP 648749, Preparation Examples).
The formula (IV) provides a general definition of the acrylic acid derivatives further to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (IV), R7, R8 and R9 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R7, R8, and R9.
The starting materials of the formula (IV) are known organic chemicals for synthesis.
The formula (III) provides a general definition of the diazonium salts formed as intermediates in the process (a) according to the invention for preparing the compounds of the formula (I). In the formula (III), R1, R2, R3, R4 and R5 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R1, R2, R3, R4 and R5; X1 preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine or bromine.
The compounds of the formula (III) have not yet been disclosed in the literature; as novel substances, they form part of the subject-matter of the present application.
The formula (Ia) provides a general definition of the substituted phenyluracils to be used as starting materials in the process (b) according to the invention for preparing the compounds of the formula (I). In the formula (Ia), R1, R2, R3, R4, R5, R7, R8 and R9 each preferably or in particular have those meanings which have already been indicated above, in connection with the description of the compounds of the formula (I) to be prepared according to the invention, as being preferred or particularly preferred for R 2, R3, R4, R5, R7, R8 and R9.
The starting materials of the formula (Ia) are novel compounds according to the invention; they can be prepared by the process (a) according to the invention.
The process (a) according to the invention is carried out using an alkali metal nitrite or alkyl nitrite. These are preferably lithium nitrite, sodium nitrite, potassium nitrite, rubidium nitrite and caesium nitrite, methyl nitrite, ethyl nitrite, n- or i-propyl nitrite, n-, i-, s- or t-butyl nitrite, n-, i-, s- or t-pentyl nitrite, in particular sodium nitrite, potassium nitrite, methyl nitrite, n-, i-, s- or t-butyl nitrite, n-, i-, s- or t-pentyl nitrite.
The process according to the invention is carried out using a hydrogen halide (HX1) or a metal halide (MX1). These are preferably hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, copper(I) chloride, copper(II) chloride and copper(I) bromide, in particular hydrogen chloride and hydrogen bromide, copper(I) chloride, copper(II) chloride and copper(I) bromide.
The process (a) according to the invention for preparing compounds of the formula (I) is preferably carried out in the presence of a diluent. Suitable diluents are generally the customary organic solvents. These include preferably aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride, dialkyl ethers such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether (MTBE), ethyl t-butyl ether, methyl t-pentyl ether (TAME), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; amides such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters such as, for example, methyl acetate, ethyl acetate, n- or i-propyl acetate, n-, i- or s-butyl acetate; sulphoxides such as, for example, dimethyl sulphoxide; alkanols such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; (monophasic or multiphasic) mixtures thereof with water or pure water.
When carrying out the process (a) according to the invention, the reaction temperatures can be varied over a relatively wide range. In general, temperatures between−20° C. and+100° C., preferably between−10° C. and+80° C., in particular between 0° C. and 60° C., are employed.
The process (a) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure—in general between 0.1 bar and 10 bar.
In the practice of the process (a) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out according to customary methods (cf the Preparation Examples).
The process (b) according to the invention for preparing compounds of the formula (I) is preferably carried out in the presence of a suitable acid acceptor. Suitable acid acceptors are generally the customary inorganic or organic bases. These include preferably alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or i-propoxide, sodium n-, i-, s- or t-butoxide or potassium n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-di-methyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-di-methyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), and 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU).
The process (b) according to the invention for preparing compounds of the formula (I) is preferably carried out in the presence of a diluent. Suitable diluents are generally the customary organic solvents. These include preferably aliphatic, alicyclic and aromatic, optionally halogenated hydrocarbons such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, di-chloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride, dialkyl ethers such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether (MTBE), ethyl t-butyl ether, methyl t-pentyl ether (TAME), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol diethyl ether; dialkyl ketones such as, for example, acetone, butanone (methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone, nitriles such as, for example, acetonitrile, propionitrile, butyronitrile or benzonitrile; amides such as, for example, N,N-dimethyl-formamide (DMF), N,N-dimethyl-acetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric triamide; esters such as, for example, methyl acetate, ethyl acetate, n- or i-propyl acetate, n-, i- or s-butyl acetate; sulphoxides such as, for example, dimethyl sulphoxide; alkanols such as, for example, methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; mixtures thereof with water or pure water.
When carrying out the process (b) according to the invention, the reaction temperatures can be varied over a relatively wide range. In general, temperatures of between−10° C. and 120° C., preferably between 0° C. and 90° C., in particular between 10° C. and 60° C., are employed.
The process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure—in general between 0.1 bar and 10 bar.
In the practice of the process (b) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required. Work-up is carried out according to customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm-killers and, especially, as weed-killers. Weeds, in the broadest sense, are all plants which grow in locations where they are undesired. Whether the compounds according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium. However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops both by the pre- and the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine encapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as extender, it is also possible to employ for example organic solvents as auxiliary solvents. Essentially, suitable liquid solvents include: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colourants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be used as such or, in their formulations, also as a mixture with known herbicides for the control of weeds, in which case ready-to-use formulations or tank mixes are possible.
Suitable co-components for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines such as, for example, atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin; others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and the use of the active compounds according to the invention can be seen from the examples below.
PREPARATION EXAMPLES Example 1
(Process (a))
A mixture of 1.8 g (21 mmol) of methyl acrylate, 1.6 g (15.5 mmol) of t-butyl nitrite, 1.6 g (12 mmol) of copper(II) chloride and 50 ml of acetonitrile is cooled to about 0° C., and a solution of 3.3 g (10 mmol) of 1-(5-amino-4-cyano-2-fluorophenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine in 20 ml of acetonitrile is added dropwise at this temperature. The reaction mixture is then allowed to warm to room temperature and stirred at this temperature for 18 hours. After the addition of 20 ml of 1N hydrochloric acid, the mixture is then extracted with ethyl acetate and the organic phase is dried with sodium sulphate and filtered. The filtrate is concentrated and the residue is worked-up by column chromatography.
2.8 g (65% of theory) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine of melting point 46° C. are obtained.
(Process (b))
0.22 g of sodium hydride (60%) are added with stirring to a mixture of 2.0 g (4.6 mmol) of 1-[4-cyano-2-fluoro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine and 30 ml of N,N-dimethyl-formamide which had been cooled to 0° C., and the reaction mixture is initially stirred for 15 minutes at 0° C., then for about 60 minutes at 20° C. and finally for 6 hours at 60° C. The mixture is then concentrated using waterpump vacuum, the residue is stirred with diisopropyl ether and the crystalline product is isolated by filtration with suction.
1.1 g (60% of theory) of 1-[4-cyano-2-fluoro-5-(2-methoxycarbonyl-ethenyl)-phenyl]-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine of melting point 154° C. are obtained.
By the methods of Examples 1 and 2 and according to the general description of the preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table I below.
TABLE 1 Examples of compounds of the formula (I) (I) Ex. Melting No. R1 R2 R3 R4 R5 R6 point (° C.) 3 H CF3 CH3 H CN 4 H CF3 CH3 F CSNH2 5 H CF3 CH3 F CN 6 H CF3 CH3 F CN 7 H CF3 CH3 F CN 8 H CF3 CH3 F CN 9 H CF3 CH3 F CN 10 H CF3 CH3 F CN 11 H CF3 CH3 F CN 12 H CF3 CH3 F CN 13 H CF3 CH3 F CN 186 14 H CF3 CH3 F CN 175 15 H CF3 CH3 F CN 85 16 H CF3 CH3 F CN 17 H CF3 CH3 F CN 18 H CF3 CH3 F CSNH2 19 H CF3 CH3 F CSNH2 20 CH3 CF3 CH3 F CN 21 H CF3 CH3 F CN 22 H CF3 CH3 F CN 23 H CF3 CH3 F CN 173 24 H CF3 CH3 F CN 159 25 H CF3 CH3 F CN 186 26 H CF3 CH3 F CN 27 H CF3 CH3 F CN 197
Starting materials of the formula (II):
Example (II-1)
0.17 g (1.2 mmol) of pivaloyl chloride is added with stirring to a mixture of 0.50 g (1.2 mmol) of 1-(4-cyano-2-fluoro-5-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine, 1 ml of triethyl-amine and 50 ml of acetonitrile, and the reaction mixture is stirred for 18 hours at 20° C. and for a further 15 hours at 60° C. The mixture is then concentrated using waterpump vacuum, the residue is shaken with IN hydrochloric acid/ethyl acetate and the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate is concentrated using waterpump vacuum and the residue is worked-up by column chromatography (silica gel, chloroform/ethyl acetate, 1:1 (v:v)).
In addition to unreacted 1-(4-cyano-2-fluoro-5-trifluoroacetylamino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine (first fraction: 0.30 g), 0.2 g (50% of theory) of 1-(4-cyano-2-fluoro-5-amino-phenyl)-3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidine is obtained as second fraction. Melting point: 195° C.
USE EXAMPLES Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After 24 hours, the soil is watered with the preparation of the active compound. It is advantageous to keep the amount of water per unit area constant. The concentration of the active compound in the preparation is immaterial, only the amount of active compound applied per unit area matters.
After three weeks, the degree of damage to the plants is rated in % damage by comparison with the development of the untreated control.
The figures denote:
0%=no effect (like untreated control)
100%=total destruction
In this test, strong activity against weeds was shown by the compounds of the formula (I).
Example B
Post-emergence test
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is chosen so that the particular desired amounts of active compound are applied in about 1000 l/ha.
0% ═no effect (like untreated control)
100% ═total destruction
In this test, strong activity against weeds such as Abutilon (100%), Amaranthus (100%), Galium (100%), Xanthium (100%), Setaria (100%) and Avena fatua (95%) is shown by the compounds of Preparation Examples 1 and 2 at application rates of 125 g/ha.
1. A process for preparing substituted phenyluracils of the general formula (I)
R 1 represents hydrogen, halogen or optionally substituted alkyl,
R 2 represents optionally substituted alkyl,
R 3 represents hydrogen, amino or respectively optionally substituted alkyl, alkenyl or alkinyl,
R 4 represents hydrogen, cyano or halogen,
R 5 represents cyano or thiocarbamoyl, and
R 6 represents one of the groupings below
R 7 and R 8 are identical or different and each represents independently of the other hydrogen, hydroxyl, mercapto, halogen or respectively optionally substituted alkyl, alkoxy or alkylthio, and
R 9 represents cyano, formyl, alkylcarbonyl, the grouping —CO—OR 10 or the grouping —CO—N(R 11,R 12 ), where
R 10 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl and heterocyclylalkyl,
R 11 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkoxy, alkenyl and alkinyl, and
R 12 represents hydrogen or represents a respectively optionally substituted radical from the group consisting of alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl and heterocyclylalkyl, or together with R 11 represents alkanediyl
characterized in that
R 1, R 2, R 3, R 4, and R 5 are each as defined above,
are reacted with an alkali metal nitrite or alkyl nitrite and with a hydrogen halide (HX 1 ) or a metal halide (MX 1 ), if appropriate in the presence of a diluent and the resulting diazonium salts of the general formula (III)
R 1, R 2, R 3, R 4 and R 5 are each as defined above and
X 1 represents halogen,
in which R 7, R 8, and R 9 are each as defined above,
in the presence of hydrogen halides (HX 1 ), if appropriate in the presence of catalysts, if appropriate in the presence of water and if appropriate in the presence of the organic solvent employed initially, or
in which R 1 R 2, R 3, R 4, R 5, R 7, R 8, and R 9 are each as defined above,
but where at least one of the radicals R 7 /R 8 represents hydrogen and at least one further radical R 7 /R 8 in a position vicinal to the first represents halogen
4812164 March 14, 1989 Wenger et al.
4859229 August 22, 1989 Wenger et al.
4979982 December 25, 1990 Brouwer et al.
5084084 January 28, 1992 Satow et al.
5154755 October 13, 1992 Satow et al.
5169430 December 8, 1992 Strunk et al.
5981436 November 9, 1999 Drewes et al.
6057269 May 2, 2000 Klintz et al.
0 255 047 February 1988 EP
WO 93/06090 April 1993 WO
Filed: Jan 16, 2001
Date of Patent: Sep 24, 2002
Assignee: Bayer Aktiengesellschaft (Leverkusen)
Inventors: Roland Andree (Langenfeld), Mark Wilhelm Drewes (Langenfeld), Markus Dollinger (Leverkusen), Hans-Joachim Santel (Leverkusen)
Primary Examiner: John M. Ford
Attorney, Agent or Law Firm: Norris McLaughlin & Marcus
Current U.S. Class: At 2-position And At 4- Or 6-position (544/309); Additional Hetero Ring Which Is Unsaturated (544/310); 5-position Is Unsubstituted Or Alkyl Substituted Only (544/312); Halogen Attached Directly To The Diazine Ring By Nonionic Bonding (544/313); Additional Chalcogen Attached Directly Or Indirectly To The Diazine Ring By Nonionic Bonding (544/314)


Travel through the unending universe and connect gems in this cosmic puzzle.
Easy to learn, tough to master; this cosmic puzzle game will keep you entertained and challenged. A field of multi-colored gems grows before your eyes, and you have to line them up in groups of three or more to make them disappear. Destroy enough gems to get to the next level and get as many points as possible. Travel the puzzling universe!


text:
Cloud Leadership
Montreal filmmaker takes SXSW interactive awards
ITBusiness Staff
Published: March 15th, 2012
An interactive film designed to be driven by a viewer's mouse clicks bagged the Interactive Arts Ward in the South by Southwest (SXSW) Festival, an annual music, film and interactive conference held in Austin, Texas.
BLA BLA, by Vincent Morisset, a Montreal, Que-based filmmaker known for his interactive video collaborations work with the rock band Arcade Fire, is an interactive tale in six parts which has characters created by both traditional and high-tech methods. The film was produced with the help of the National Film Board of Canada.
BLA BLA was one of the winners of an Entertainment Award in the annual Communication Arts Interactive Competition. The SXSW event is a hugely popular arts and technology conference attended by a large number of technology startups.
A BLA BLA character
According to NFB the BLA BLA explores the fundamentals of human communications. "The viewer makes the story possible: without him or her, the characters remain inert, waiting for the next interaction."
With the use of a mouse device, the viewer's clicks and searchs makes the movie move forward. Each of the six chapters depicts a different aspect of communication such as: learning a language, making small talk and expressing emotions.
"BLA uses xenography, drawing on paper, ActionScript-generated animations, puppet stop-motion combined with real-time 3D mapping etc," Morisset said..
"I am inspired by projects that feel free aesthetically. I wanted BLA BLA to feel hand-made, imperfect, fragile, so we forget about the technology," he added.
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A questionnaire survey on the status of intelligent building development was carried out. Based on actual survey questionnaire data, the development status of technology and applications was described in this paper, mainly discussing the existing problems and the proper future development. It is aimed at providing valuable findings on intelligent building development, exploring an innovative way to build a practical, reliable, and easy-used intelligent system to meet the requirements of users. Among all the designing aspects, the configuration of both hardware and software is the most tedious and error-prone part when building an intelligent system, as a huge workload is inevitable when solving the difficulties on system transformation. Unsuitable operation logic of the system and equipment is another problem, as the distance between the original expectation of the intelligent system and the real operation effect is still large. Though some building systems realize integration between the subsystems, they work independently, thus enabling different subsystems to work as a whole is another problem which needs to be emphasized. A much simpler configuration process or structure of the software and hardware system is significantly required in this field. If the controller could adapt its own operation logic automatically according to preset equipment parameters, this problem might be solved fundamentally.


The SAP "all-in-one" solutions with global coverage for hotel business operations.
Integrated solutions for the reporting and assessment of all operations of a chain.
The solution to explode in a fully integrated way with PMS, the online channels for B2C and B2B.
More than 380 hotels in 28 countries will transition from a multivendor environment to Indra's unified TMS platform, setting a new course for multi-property technology adaption across the globe.
© 2016. Indra Sistemas, S.A. All right reserved.
Not only will the TMS suite pave the way to higher levels of guest service and more efficient operations, but it will enable us to access much more accurate guest information from any property, any department, anywhere in the world, and in real time from a single database. Streamlining technology is a step forward in maximizing efficiency across our organization and tightening our bottom line.
Due to the open nature of Indra's modular and configurable Travel Management Suite, we are now able to efficiently and effectively make chain-wide policy decisions that keep us competitive, with a quick time-to-market response and a minimum investment. Unified information and one data structure is truly driving our business intelligence, which has contributed to increased guest satisfaction, loyalty and revenues.
Indra is dramatically changing the technology landscape, not just by giving hotels an alternative holistic, all-in-one solution for hotel chain management, but by developing modules so comprehensive that they stand on their own - and stand head-and-shoulders above their competition.
One of the top 25 hotel chains in the world is directing the future of hotel technology by migrating to an all-in-one, unified platform for hotel chain management. Using Indra's SAP-based ERP, NH Hotel Group will now operate with an integrated approach to hotel chain management and blend all back-office, front-office and CRS needs on a single technology platform.
NH Hotel Group, Europe's third-ranked business hotel chain with close to 400 hotels in 28 countries across Europe, the Americas and Africa, is migrating all key systems to the Indra Travel Management Suite — TMS Platform. This includes transitioning all its core front office solutions, including PMS, CRS, Loyalty, Business Intelligence, Sales & Catering, Spa, Website and CRM. In addition, all back-office administrative systems will be converted to Indra's TMS for ERP solution based on SAP ERP, covering finance, sales, management control, procurement, asset management, invoicing and HR modules.
The brand-wide roll out began in January 2014, in Spain and will extend to more than 20 countries in Europe and America. In the same timeframe Indra will develop and launch NH's new website to make it a key marketing and business generation tool. The new TMSforWeb web platform, based on SDL Tridion CMS, will be optimized to improve the experience of returning hotel guests and to attract new ones. A new loyalty program, NH Hotel Group Rewards, also is being launched in cooperation with Indra, designed to bring the brand closer to its guests and surprise them during each stay with exclusive services and personalized offers. NH Hotel Group Rewards will be powered by the TMS Loyalty module.
Alu Rodriguez, NH Hotel Group CIO, said she believes the way to honor the company's commitment to personalized service is to minimize the number of different systems across all NH hotels and replace them with seamless, uniform technology.
"This is where Indra comes in," Rodriguez said. "Not only will the TMS suite pave the way to higher levels of guest service and more efficient operations, but it will enable us to access much more accurate guest information from any property, any department, anywhere in the world, and in real time from a single database. The marketing potential is huge when you have such a complete and accurate database. Streamlining technology is a step forward in maximizing efficiency across our organization and tightening our bottom line. We are impressed with the successes other businesses have had with SAP, and we are eager to get started with Indra and begin maximizing results."
Indra is the leading Spanish consulting and technology multinational and one of the top companies in Europe and Latin America. SAP is the No. 1-ranked ERP business platform with 25.5 percent worldwide market share. Indra's TMS solutions support all the business needs of a hotel chain or management company in one comprehensive system, hosted in the cloud or on-premise. Each module of the TMS suite is also available separately, and hoteliers can take advantage of Indra's unparalleled interface capabilities to integrate these powerful applications with their existing systems from other vendors.
Indra is a member of the exclusive club of SAP® Global Partners, composed of approximately 30 multinational providers delivering consulting services for SAP solutions. Indra's SAP expertise, extensive relationship with SAP partners, swift time to market are just part of the reason that NH Hotels decided to move to an all-in-one, fully integrated enterprise solution. The system's flexibility, along with its multinational/multilingual/currency conversion capabilities also spoke volumes.
"We are honored to add NH Hotel Group to our global portfolio of hotel customers said Connie Rheams, Indra senior vice president. "When such a large, prestigious global chain recognizes the operations and financial benefits of using one technology platform across its vast enterprise, we believe it will trigger other hoteliers to review their technology investments and strategies. Indra is equipping NH Hotel Group with the most advanced technology available to deliver real-time, 'know-me' experiences. NH will be in a strong position to deliver upon its guests' expectations 100% of the time. 'Real-time segmentation,' 'dynamic offers,' 'personalization,' are not buzz words . . . they are a reality with Indra TMS platform"
About NH Hotel Group NH Hotel Group (www.nh-hotels.com) is Europe's third-ranked business hotel chain. It operates close to 400 hotels with almost 60,000 rooms across Europe, the Americas and Africa, including top destinations such as Berlin, Madrid, Amsterdam, Paris, London, Rome, Bogota, Mexico City and New York. NH is traded on the Madrid stock exchange.
About Indra Company Indra is one of the world's largest consultancy and technology multinationals, a leader in Europe and Latin America and is expanding in other emerging economies, with sales approaching €3,000 million, it employs 42,000 professional and has customers in 128 countries. At the core of Indra's hospitality practice is its Travel Management Suite (TMS), built on the world-leading SAP technology platform. The TMS services all the business needs of a hotel chain or management company in one comprehensive system, hosted in the cloud or on-premise. It offers unsurpassed functionality for any business area, and it is open, configurable, scalable and modular. Hotels can start with any of the TMS modules and add-on as needed in the future, providing a more custom approach to enterprise management. Indra's "TMS for Hotels" suite provides modules for property management, events (sales & catering), point of sale, loyalty, spa, restaurant, purchasing, finance, etc. These modules can be added over time at the customer's convenience, leveraging the platform and implementation in place. For more information on Indra's hospitality practice, contact Connie Rheams at (214) 554-3851 or email her at crheams@indracompany.com.


text:
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Nitro Ninjas
BMX Bike Games » Motorcycle Games, Stunt Games » Nitro Ninjas
Rate Nitro Ninjas:
Rating: 4.54/5 stars (1347 ratings)
Nitro Ninjas Instructions
Accelerate using the up arrow key. Move backwards using the down arrow key. Lean backwards on your bike using the left arrow key. Lean forward on your bike using the right arrow key. Perform tricks using number keys 1-4. Jump using 'space'.
Bike Champ Pencil Racer 3: Drive It TG Motocross 3 Pencil Racer Uphill Rush 2 Uphill Rush Motobots
Nitro Ninjas Walkthrough
Nitro Ninjas is the type of BMX game that focuses on the action and everything you love about BMX games without throwing in a lot of extras to make the game seem more complicated. Your goal is simple. Make it from the starting line to the finish line without crashing or running out of time. Along the way, you'll have to navigate over a variety of obstacles like gaps in the track, hills, bowls and even loops all while doing everything you can to keep your wheels on the ground. With that said, there are enough little added touches to make the game feel unique and original but not so many that you're overwhelmed with additional goals and features. The focus of this game is on the riding and that's really what makes it so appealing to die hard BMX game fans.
In Nitro Ninjas, staying in control of your bike at all times is vital, but that's not always easy to do. You're moving fast, as you would in most BMX games, but the difference here is that balancing your bike by leaning back or forward is actually pretty tricky. If you lean too far forward or too far back you'll crash, but avoiding that is difficult. You really need to be careful and pay attention. In many cases, you'll have to lean in one direction and then immediately lean in the opposite direction to get yourself in a steady position. Meanwhile, the clock is ticking, so you don't really have the time to slow down. Many of the other BMX games online shy away from giving you a time limit to complete the level because it makes a game much more difficult, but that's the beauty of this one. It isn't afraid to give you a real challenge and put your skills to the test. For that reason, experienced BMX game players that are looking for a challenge will absolutely love this game.
In addition to trying to avoid crashing and trying to make it to the end before time runs out, Nitro Ninjas also offers a few extras to make the game more entertaining. First, there is the addition of ninja style stars you can collect as you play to boost your score. Getting the stars will require a little work - and most times a little jumping, but they're an interesting addition. Newcomers to BMX games are probably going to have enough trouble getting through the levels without trying to collect the stars so it might be a better idea to just collect them with you can. More experienced players, on the other hand can really challenge themselves by trying to collect all of the stars in a level. It's hard to do, but it gives the game a whole new level of difficult. Aside from the stars, you can also perform four different tricks as you ride. I would recommend only trying to perform tricks when you get a lot of air off a ramp or a jump. If you don't have enough room to land your jump you will not only not get points for the trick, but you'll also likely crash. You only have ten lives to get through the game with. Don't waste them trying to perform tricks when you don't have the room to do so.
Overall, Nitro Ninjas is an excellent game for any fan of BMX games regardless of skill or experience level. It's entertaining and challenging without being overly complicated or hard to understand. Newcomers will have a hard time avoiding crashes when they first begin playing because it can be extremely hard to keep your bike under control, but as long as you pay attention and have your fingers ready on the arrow keys, you should be able to get the hang of it. More experience players will love this one because not only is the game itself challenging but the tricks and stars offer an even higher level of difficulty should they choose to pursue it. One of the best ways to get a high score is to not only do the tricks that require hitting the number keys, but also to perform back flips as often as possible by hitting the left arrow key until your bike flips. You'll need the room to land the flip just as you would with any other trick, but you'll also be rewarded with a decent point bonus. If you like BMX games and are looking for a challenge, this is a game you simply can't pass up.
Top 10 BMX & Bike Games
#1. BMX Master
#2. Free Rider 2
#3. Military Rush
#4. BMX Extreme
#5. Icycle
#6. Construction Yard Bike
#7. BMX Pro Style
#8. Dirt Bike 2
#9. Drag Bike Manager 2
#10. Trial Bike Pro
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This two day workshop aims to increase your understanding around anxiety, its causes, how to manage unwanted feelings and better manage physical symptoms associated with anxiety as well as enabling you to change unhelpful thoughts and behaviours which can feed into anxiety.
These free workshops are part of Derbyshire Mind's Enjoying Derbyshire project and are delivered and facilitated by Derbyshire Federation for Mental Health.
Please contact Derbyshire Federation for Mental Health to book your place.
There will be an hour's break for lunch.


text:
Italian radish prices and demand are dropping
Between November and April, società agricola De Simone in Francolise (CE) produces different types of radishes available in various types of bunches and packets (bags, without leaves, Ifco). Over the past two years, the company has grown in terms of both facilities and processing.
70% of our production is already allocated and destined abroad, while the remaining 30% is available. De Simone mainly works with foreign distribution chains, but it does work with some Italian retail chains supplying radishes in 125, 250 and 300 gram bags.
The company owns 60 hectares of covered crops as well as 40-50 hectares of open-fields. "We started harvesting winter varieties in late October. The high temperatures of up until a couple of weeks ago caused a few leaf problems. Prices and consumption are dropping, also due to the situation created by the Coronavirus, which pushes consumers to think about it more when making a purchase. Luckily, demand for our radishes is held up by the fact that our products are almost zero-residue."
"We mainly export to Germany, where we supply Lidl stores, but also to Austria, Czech Republic, Switzerland, Poland and Romania. Each chain has its own specifications when it comes to packaging: for example, when it comes to wooden or plastic crates, Germany prefers sizes 8x15, 10x15 or 15x15, while Poland, Romania and Switzerland opt for size 20x10."
Due to Covid-19, labor is reduced. "As we work with mainly non-EU workers, those who went home during the summer had difficulties coming back to Italy, so we have had to employ the locals."
In the summer, between June and August, the company focuses on watermelons and mini-watermelons (seeded and seedless). Se Simone is also working on a leafless radish project.
Aldo De Simone
Società Agricola De Simone S.S.
Via C.S. Bottacce, 18
81050 Francolise (CE) - Italy
Email: agricoladesimone@gmail.com


text:
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/**
 * Change the visibility of the current property on a table.
 * @param bool
 * @decorator
 * @formio
 * @property
 * @schema
 */
export function TableView(bool: boolean): PropertyDecorator {
  return Component({
    tableView: bool
  });
}

redpajama_set_name: RedPajamaGithub


Latimer County is named for James S Latimer, who was a member of the Oklahoma Constitutional Convention.
Description: The building faces east and is a two story course stone structure. The center section rises higher than the north and south wings. The central entrance is framed with concrete trim. The roof line is flat. The building was constructed as a Works Project Administration project using local trades. The building was remodeled in 1968. The architect was Morgan-Tyson-Mills & Associates of Tulsa and the contractor was Bloomfield Construction Company.
Note: In 1915, the courthouse occupied the Great Western Coal & Coke Building at 701 East Main Street which was remodeled.
See: The architect, Forest Butler of Oklahoma City, designed courthouses in Custer County, Pontotoc County and Pushmataha County.