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English into Spanish Translation
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Whitepaper hyperspectral remote sensing
A novel technology for crop monitoring. How does it work? And what are the benefits?
Hyperspectral remote sensing is the latest advancement in crop monitoring and precision agriculture. It allows farmers to 'see' in their crops and gives them the knowledge what the conditions of their crops are, what biological processes are occurring and what actions are need to be made before going into their fields. But before going in-depth on hyperspectral remote sensing. What is remote sensing in the first place?
What is Remote sensing?
Remote sensing can be best described as: "The science and art of obtaining information about an object, area, or phenomenon through the analysis of data acquired by a device that is not in contact with it."
Its applications dates back to world war 1, when it was crucial to know what happened behind enemy lines, how cities and infrastructure looked like and where strategic places were localized. This information was acquired by attaching cameras to homing pigeons, which were already used to convey written messages. From these images, soldiers could get valuable information about the ground situation and to know the best timing to succeed in their missions.
Nowadays, the 'pigeon-technology' has improved immensely. Our vehicles of sensing technologies are: satellites, airplanes, drones, robotics, hand-held devices and sensor technologies. Each having its own benefits. A satellite or airplane can cover a large area quickly, but with little intervals, low resolution and little detailed information. Information from satellites or airplanes remains therefore sample based and is little actionable. A robot or sensor however, can gather specific and very relevant information about an object with many intervals, but it is mostly stationary or covers small areas.
Also, we do not have to solely rely on 2D images anymore. New technologies are still being developed to gather more information of an object remotely. One of these major advancements is the commercial use of spectroscopy. Spectroscopy allows the user to measure the energy of a specific wavelength (color) within the electromagnetic spectrum that is emitted, absorbed, or scattered by an object at one single point. These spectral signals can give information about a property or feature of an object.
What is Hyperspectral imagery?
Normal cameras can see 3 bands of colors within the visible spectrum: red, green and blue. Instead of just these three colors, hyperspectral imagery uses specially engineered sensors that measure the entire spectrum of light in the visible, but moreover also in the non to human visible spectrum for each pixel in an image. The entire spectrum is then divided into 100+ color bands.
Each band is analyzed and used to make a multi-spectral colored dataset in the shape of a cube that contains three dimensions of information about a subject: 2 dimensions of spatial information and a 3rd dimension of spectral information. By analyzing all colors of the spectrum in each pixel, we can obtain the unique spectral 'fingerprint' of an object. These fingerprints deliver very detailed information about the state and constitution of the imaged object.
There a multiple applications of hyperspectral imagery in many different industries such as: Image guided surgery, mineralogy, optical sorting, food quality inspection and forest monitoring. Still, agriculture and precision agriculture is the largest sector for hyperspectral imagery where most of the developments are being made.
What are the benefits?
Especially in agriculture, most of the inspection relies on human inspection. As mentioned, the human eye can only see a small portion of visible spectrum. There is thus a clear limit to what we as humans can view in the world around us. For us humans two leaves can look identically green. But when using hyperspectral imagery we obtain more information in the non-visible spectrum which allows us to still distinguish between these two leaves on their properties.
Moreover, things as plant stress as nutrient deficiency and diseases become visible to the human eye when the damage is already done. Using hyperspectral imagery, the spectral specific fingerprints of plant stress become visible in the most early stages. This allows farmers to be more efficient with resources, achieve higher yield and prevent crop losses and ultimately reduce their environmental footprint.
At Polariks, we are specialized in high resolution hyperspectral remote sensing and continuous crop monitoring. Interested to find out what potential hyperspectral imagery has for your organization? Please contact us at firstname.lastname@example.com.

subset: commoncrawl


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I'll post more as soon as I get more details!!!!!!!
"Ouran High School Host Club" to get a movie adaption
Today, TBS held a fan event for their midnight drama "Ouran High School Host Club" with the whole cast, including lead actress Kawaguchi Haruna and actor Yamamoto Yusuke. At the event, they also revealed that the drama is going to be made into a movie that is scheduled to open in March of 2012.
The drama and upcoming movie are based on a popular manga of the same name by mangaka Hatori Bisco. The story is a romantic comedy centered around the popular host club of the 'Ouran High School', where the female scholarship student 'Haruhi' (Kawaguchi) has to disguise herself as a male host in order to pay for the expensive vase she broke while visiting the club for the first time.
Sony Pictures Entertainment is going to distribute the movie. It will be their first distribution of a movie adaption from a TV drama.
Kawaguchi is already enthusiastic about the movie adaption and commented, "I'm already all fired up as this is going to be my first starring role in a movie. I will work hard once the filming begins and hope that I will be able to show you some new faces you haven't seen in the drama so far."
Meanwhile Yamamoto declared, "In the drama we had to be careful not to go too far and I only put in 60% of what I would be capable of, but in the movie, without any restrictions, I'd like to raise the bar up to 120%."
For the aforementioned fan event, titled 'Ouran High School Host Club Summer Party', they invited 100 fans of the drama to visit the cast at the actual set. They were able to throw questions at Kawaguchi, Yamamoto, and the rest of the cast, and participate in a lottery for some exclusive presents.
Keep your eyes on Tokyohive, as we will keep you updated with more information about the movie as soon as more details become available.
source: tokyohive
Last edited by yanie on Fri Aug 26, 2011 3:18 am; edited 2 times in total


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Riding the Olympic Boom
Vendors' Shares Rise, But Scrutiny Hurts a Few
BEIJING -- It isn't just athletes who are trying to soar at the Olympics. High market expectations surrounding the 2008 Games are buoying the shares of companies involved, from makers of towels to towers.
But publicity from an Olympic role isn't a guaranteed plus. Increased attention from activists can add scrutiny -- and risk -- for those hoping to ride the Olympic boom.


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Marketing is always evolving and changing. With fewer people turning to their TV sets for entertainment and more of a push going towards streaming services, a lot of the old, accepted rules and norms in marketing are fading away.
Digital marketing has usurped traditional marketing in so many ways. Unfortunately, many CEOs and business owners are stuck in the past and are relying on outdated marketing techniques which won't work anymore.
People have wised up and become more conscious of doing business with companies that put forth the effort to provide them the best value and information. Furthermore, the way people are interacting with brands has also dramatically changed.
Who needs to watch an ad or read an ad in the paper when someone can just as easily send a company a tweet or leave a review on Yelp or TripAdvisor? Access and convenience have become a more prominent part of marketing because when people have issues, they want to get a hold of someone at a company online quickly.
They don't have much time to spend calling your company and waiting a long time to get to a customer representative. With this in mind, there are marketing tactics and strategies which are antithetical to the current trends in marketing you should completely forget about and for a good reason.
1. Still Relying Heavily on Paper
We live in a digital world powered by websites where you can post information about your company. It makes no sense to keep printing a massive chunk of your advertising and promotional material when you could create a PDF and post it on your website instead.
By making the switch to digital, you save thousands of dollars in marketing costs, not to mention this is better for the environment too. How about that? Saving money while protecting the environment: one of the many reasons digital marketing is great for businesses.
2. Advertising on Television
According to the Pew Research Center, 61% of adults in the United States use streaming services to get their entertainment. Only 31% of them are watching TV at all. There's not much of a point in creating ads for TV when hardly anyone's watching anymore.
If you want to advertise, a much better route would be to use Google Ads and Facebook Ads. These platforms help you market to people who spend a lot of their time on the internet. Millions of people are browsing YouTube, Google, and Facebook. To many, the internet has become like their TV because they can watch whatever they want without having to pay hundreds of dollars a month on cable or satellite TV bills.
3. Cold Calling
Cold calling is one of the worst ways to get new clients. With people already on guard getting phone calls from telemarketers, they are likely to hang up or never look at your business again. HubSpot says that cold calling fails 90% of the time.
It takes hundreds of phone calls just to make a sale, yet many companies still funnel much of their marketing budget on cold calling. Another reason cold calling isn't that effective is that you don't have enough time to establish a trusting relationship with customers.
With SEO and content marketing, you don't need cold calling anymore. These digital marketing strategies help you get found on Google by your audience. You can offer much more value on your website and compelling reasons for people to buy from your company that way than through cold calling.
4. Billboard Advertising
Billboards are very expensive and can run a business up to $4000! For less than that price, you can have a professional web design company build your company a new website, run social media marketing campaigns, set up Google Ads, implement an SEO strategy, and much more. You're better off saving the money for things which are going to guarantee returns in the long run.
There are lots of other problems with billboard advertising beyond the cost. People driving on the road are going to be focused on driving, so the chances of them remembering much from your ad are slim. Georgia's recent hands-free law enacted last month has also added more pressure for drivers to pay more attention to the road too.
You can accomplish the same objectives with landing pages for your lead generation strategy instead. With landing pages, people will have more time to digest your message, and there's way more opportunity to capture valuable information.
By providing excellent offers and creating more value than your competition, lead generation through landing pages is feasible. Through landing pages, you can also establish a stronger local SEO presence helping you get found by people living in the areas you're offering services in.
5. Using a Phone Book
Believe it or not, people are still getting phone books delivered to their homes, specifically in more rural areas. The problem centers back to how with a simple Google search, people find products and services they need in a matter of seconds. There's no time spent trying to flip from page to page finding a business quickly.
Local SEO has dethroned phone book marketing as the way to market your business to people. By building strong business citations and a well-crafted Google My Business listing, you give your customers a better way to contact you.
With a Google My Business listing, customers can leave your company positive reviews you can use as social proof to generate more leads. Google will also rank your business and website higher with these positive signals present.
6. Sending Customers Physical Mail
A big problem with sending people physical mail is there's no way to keep track of who opens them or any way to objectively measure your conversion rates. Now with email marketing and powerful tools as MailChimp and InfusionSoft, you can instead build a list of potential leads from an email list.
It's best to make your list from people who have already subscribed to a newsletter or service you provide. You'll run into the same problems as snail mail sending emails to people who don't have any interest or prior connection to your company's services. Worse, your emails will be marked as spam either by them or the email provider.
7. Neglecting the Blog
Don't underestimate the power of blogging. By blogging at least a few times a week, you give Google a reason to come back to your website and index new pages helping you get found for relevant search results.
There's lots of wiggle room to talk about the issues affecting your industry and answer customer questions. Lastly, you'll have more of what you need to launch effective social media marketing campaigns.
8. Not Updating the Website
Best practices in web design are always changing, and it will become apparent to website visitors that your website hasn't kept up with the times. Older sites aren't going to be responsive on all devices and browsers. Your old website may not have the most secure web hosting either.
More websites are using HTTPs instead of HTTP because it keeps their customers' personal information much safer. Lastly, if your website looks ugly and unappealing, people will quickly find other business websites to visit.
9. Not Taking Time to Create a Digital Marketing Strategy
Digital marketing won't be practical for your business without a strategy and a plan in mind. Some business owners catch onto to the idea of digital marketing but have no clue where to start or how to make it work for their businesses. The primary job of a CEO of a firm is not to spend time writing content or running Facebook campaigns. They need to be entirely focused on running the day-to-day aspects of the business. There's not much time to get involved in developing the digital marketing strategy.
That's why it's best to let an experienced digital marketing agency in Atlanta handle the work.
Our professional digital marketers at Viridian Geeks are experienced in developing custom digital marketing and SEO strategies for businesses. They will perform keyword research and study your competition to create digital marketing strategies to match what your target audience wants.
Call 470-440-3434 or email [email protected] to get started. You can also learn more about digital marketing, web design, and SEO by reading our blog where we post new content each day!


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- Vodafone and Snapchat partner to raise awareness of teen cyberbullying, with #BeStrong anti-bullying emojis appearing as Geofilter photo overlays for millions of 'Snapchatters' across Europe.
- Millions of UK 'Snapchatters' will be able to use the Geofilter overlays to show support for Anti-Bullying Week.
- #BeStrong emojis created in response to global cyberbullying survey among 5,000 teens, which found one in five teens cyberbullied, a fifth of those felt suicidal and almost half struggle to find the right words to support friends bullied online.
- Vodafone Foundation to donate £1 per retweet or like of the #BeStrong emojis* on Twitter or Facebook to anti-bullying charities during Anti-Bullying Week in the UK.
Snapchat, the mobile platform with over 100 million global daily active users, has partnered with Vodafone to help raise awareness of teen cyberbullying during the UK's Anti-Bullying Week 2015.
Snapchat has created a series of Europe-wide Geofilters – special artistic overlays for 'Snaps' that can be accessed from select locations – to encourage 'Snapchatters' to take a stand against bullying by sharing Snaps featuring Vodafone's #BeStrong emojis. The images will reach millions of Snapchatters all across Europe to help them take a stand against bullying.
The #BeStrong emojis were designed in response to an 11-country survey commissioned by Vodafone from YouGov*, where 72% of the teenagers surveyed said they would welcome an emoji they could share with friends being bullied online to show their support.
The #BeStrong emojis were developed in collaboration with anti-bullying ambassador Monica Lewinsky. Lewinsky, whose TED Talk about bullying has had more than six million views, first brought the idea for the #BeStrong emojis to Vodafone. Others who helped create the #BeStrong emojis include Berkeley University Professor Dacher Keltner – the psychologist who advised on the creation of the characters for Pixar film Inside Out, semioticians (who study signs and symbols and their use or interpretation) and anti-bullying NGOs including The Diana Award and ENABLE, a European Union project to help combat bullying.
Commenting in a video, Professor Keltner explained the importance of teens being able to offer support and show sympathy to their peers being cyberbullied. He said: "A lot of emojis can be limited for communicating emotions. The bystander needs better tools. Specific emojis that they can send their friends to show that they are there for them."
The global cyberbullying study, one of the largest of its kind, revealed that more than half of teenagers said cyberbullying is worse than face-to-face bullying and 43 per cent believe it to be a bigger problem for young people than drug abuse. Additionally, 38 per cent said they did not tell their parents or guardians, as they felt ashamed (32%), scared their parents would get involved (40%), or worried what their parents might do (36%).
In addition, the Vodafone Foundation, Vodafone's philanthropic arm, as part of its digital family programme, is also helping to raise funds for anti-bullying NGOs by donating £1(€1.40) for every Twitter retweet or public Facebook like of Vodafone's image of the #BeStrong emojis* during Anti-Bullying Week in the UK.
Snapchat's Director of Public Policy Micah Schaffer, said: "We're proud to leverage our Geofilters product to help spread the BeStrong message with 'Snapchatters' across Europe. We hope that sharing this message can help 'Snapchatters' take a stand against bullying on our platform and beyond."
Vodafone Foundation Director Andrew Dunnett, said: "The new generation that was born digital thrives in a world of constant connectivity, but there are clear risks for young people as well as benefits. Our research showed many teenagers find it difficult to help their friends when cyberbullying is happening, and the #BeStrong campaign has been created to help them convey emotional support."
The initiative is a continuation of Vodafone's commitment to helping children and their parents navigate through the social and digital world in a safe way. Vodafone UK recently released the fourth edition of its Digital Parenting magazine, developed in partnership with The Parent Zone, which is full of tips of how to help young people stay connected safely. Since its release in September, more than 500,000 copies of the magazine have been distributed to schools, NGO's, government bodies, children's charities and other outlets. Vodafone is also the headline sponsor of the upcoming National Theatre production, wonder.land, which highlights a range of issues relevant to many teenagers today, particularly the positive and negative impacts of the online world.
Note to editors:
- Images of the emojis and video content can be found here https://www.flickr.com/gp/vodafonegroup/pK5215
- Survey highlights across the 11 countries can be found here http://www.vodafone.com/content/dam/group/media/downloads/15-09-22-Cyberbullying-FINAL.pdf
- Vodafone and NGO The Diana Award have also released a series of learning modules aimed at teenagers, which cover subjects from 'selfies 'and 'online gaming' to 'social networking' and'mean tweets'. Further learning modules will be released over the next year on vodafone.com/parents, which include advice for parents.
- *All figures, unless otherwise stated, are from YouGov Plc. Total sample size was 4,720 13-18 year olds in the UK, Germany, Italy, Spain, Netherlands, New Zealand, Greece, South Africa, USA, Ireland & the Czech Republic. The figures have been given an even weighting for each country to produce an 'average' value.
- *The Vodafone Foundation will provide a total donation to anti-bullying NGOs of up to £100,000 (€137,000)
- A summary of an anti-bullying round table held on 17 November to launch the partnership can be found here.
Vodafone UK Media Relations
01635 666777
About Vodafone UK
Vodafone UK is part of Vodafone Group, one of the world's largest telecommunications companies, and provides a range of services including voice, messaging, data and fixed communications. Vodafone Group has mobile operations in 25 countries, partners with mobile networks in 46 more, and has fixed broadband operations in 18 markets. As of 31 March 2018, Vodafone Group had 535.8 million mobile customers and 19.7 million fixed broadband customers, including India and all of the customers in Vodafone's joint ventures and associates. For more information about Vodafone UK, please visit: www.vodafone.co.uk
Vodafone UK partners with businesses of all sizes – from start-ups and small businesses to the largest corporates and the public sector. The company has worked with UK businesses for over 30 years, starting out as a mobile provider and becoming one of the UK's leading total communications partners. It provides a range of voice and data services, secure communications infrastructure, fixed and contact centre capability, and unified communications, and was the first mobile phone operator to offer a truly converged service for fixed and mobile.
Vodafone UK
Vodafone House, The Connection, Newbury, Berkshire RG14 2FN, England
Vodafone UK Media Relations
Telephone: +44 (0) 1635 693 693Twitter: @VodafoneUKNews
Vodafone Limited
Registered Office: Vodafone House, The Connection, Newbury, Berkshire RG14 2FN
Registered in England No: 1471587


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(a) isomerizing 2,3,4,3',4'-penta-O-acetyl sucrose to 2,3,6,3',4'-penta-O-acetyl sucrose;
(b) chlorinating the isomerized acetate at the 4,1' and 6'-positions; and
(c) deacetylating the resulting chlorinated product; the isomerization step (a) being effected by treating a solution of 2,3,4,3',4'-penta-O-acetyl sucrose in an inert solvent with a weak acid at an elevated temperature.
|Method of preparation of 2-chloro-2-deoxysaccharides
|Khan et al.
|Preparation of sucrose 6,6'-dichloro hexa-acetate
|Khan et al.
|1-N-((S)-α-substituted-ω-aminoacyl)-neamine or -ribostamycin and the production thereof
|Akita et al.
(where R1 and R2 represent phenyl groups and R3 represents a phenyl group or a polystyrenebound phenyl group) and carbon tetrachloride; in an organic tertiary amine base and at a temperature of from ambient to the reflux temperature of the system.
(in which X represents a hydrogen atom or a methyl group and R represents an alkyl group) in an inert solvent.
(in which Y represents an aryl group or an aryloxy group).
This invention relates to a process for the preparation of 2,3,6,3',4'-penta-O-acetyl sucrose and, hence, the preparation of the potent sweetner 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose or, properly, 1,6-dichloro-1,6-dideoxy-β-D-fructofuranosyl 4-chloro-4-deoxy-α-D-galactopyranoside. The above mentioned trichlorogalactosucrose, hereinafter referred to as TGS, is a potent sweetener having a sweetness several hundreds of times that of sucrose. Its use as a sweetener and sweetening compositions containing it are disclosed in British Patent Specification No. 1,543,167.
The main problem in the synthesis of TGS concerns the chlorination of the 4,1' and 6' positions of a sucrose molecule without chlorination at other positions. One way of achieving this is to chlorinate a sucrose derivative having the 2, 3, 6, 3' and 4' positions blocked, conveniently by esterification, so that only the 4,1' and 6' positions are available for chlorination. The chlorination of such an intermediate is complicated by the fact that, of the three hydroxy groups to be replaced by chlorine atoms, one is a reactive primary hydroxy group (the 6'-group), one is a considerably less reactive primary group (the 1'-group) and the third is a secondary hydroxy group.
The route disclosed in the literature (Fairclough et al., Carbohydrate Research, 40 (1975) 285-298) involves the formation of the 6,1',6'-tritrityl derivative of sucrose followed by peracetylation of the molecule. The tritrityl penta-acetate obtained is then, in one stage, de-tritritylated under conditions which cause a migration of the acetyl group at the 4-position to the 6-position vacated by one of the leaving trityl groups. This detritylation reaction was first reported by McKeown et al. (Canadian Journal of Chemistry 35 (1957) 28-36) and involves dissolving the tritrityl penta-acetate n glacial acetic acid and heating for the required time. Under these conditions, the yield of detritylated pentaacetate is generally not greater than about 55% of theory, the low yield apparently being caused by the formation of various competing by-products. MKeown et al. reported that an optimum yield could be achieved by refluxing for about 30 minutes. Any less or any more time led to a reduction in the yield, until at 120 minutes reflux substantially no desired product was obtained.
An alternative procedure for achieving the migration of the 4-acetyl group to the 6-position was demonstrated by Bredereck et al., (Chem.Ber.,) 91 (1958) 2824). In this two-stage procedure the tritrityl penta-acetate was first selectively detritylated by reaction with hydrogen bromide in acetic acid in the cold to give the non-isomerised penta-acetate. This, in turn, was treated with glacial acetic acid at an elevated temperature to obtain the isomerised penta-acetate in a relatively low yield (24%). The overall yield for the reaction from the tritrityl penta-acetate to the isomerised penta-acetate was about 19%.
From these publications, it appears that the combined detritylation and acetyl-migration gives a better yield of the isomerised penta-acetate than separate detritylation and subsequent isomerisation.
We have now found, surprisingly, that selection of specific reaction conditions for the acetyl migration step can give considerably higher yields overall for the two-stage process than the one-stage combined process.
According to the present invention, there is provided a process for the production of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose including the steps of (a) isomerising 2,3,4,3',4'-pentaacetyl sucrose to 2,3,6,3',4'-penta-O-acetyl sucrose; (b) chlorinating the isomerised acetate at the 4,1' and 6'-positions; and (c) deacetylating the chlorinated product; characterised in that the isomerisation step (a) is effected by treating a solution of 2,3,4,3',4'-penta-O-acetyl sucrose in an inert solvent with a weak acid at an elevated temperature.
The weak acid is preferably a carboxylic acid, especially an aliphatic carboxylic acid such as acetic acid. In general any acid having an acid strength of the same order as acetic acid under the conditions used, will suffice.
The reaction temperature should be elevated above ambient temperature in order to provide an acceptable reaction time. In general, a temperature of from about 80° to 150° C. is suitable, preferably 100° to 130° C.
The inert solvent is any solvent for penta-O-acetyl sucrose which remains liquid at the elevated temperature selected, e.g. a temperature in the range of 100° to 140° C. Ketonic solvents are particularly preferred, especially methyl isobutyl ketone, which refluxes at about 126° C. Ester solvents of sufficiently high boiling point are also useful, e.g. n-butyl acetate. Also of particular interest are aromatic hydrocarbons such as toluene or xylene.
A dilute solution of the acid in the solvent is suitable, e.g. a solution of from 2 to 10% by weight, especially about 5%. This degree of dilution is suitable for reaction with the sucrose penta-acetate dissolved at a concentration of up to 30% by weight, e.g. about 20%.
The reaction time naturally depends on the temperature chosen, but at a temperature of about 110° to 130° C. a reaction of 2 to 4 hours has been found satisfactory.
In the reaction according to this invention, a yield of at least 75% of theory can be achieved in step (a). Since the detritylation of 6,1',6'-tritritylsucrose penta-acetate (without migration) can be achieved in well over 90% yield, this gives an overall yield from the tritrityl penta-acetate of about 70%. Detritylation of 6,1',6'-tritrityl sucrose pentaacetate can be effected simply by treatment with acid in an inert solvent at a low temperature, e.g. about 0° C. Thus, for example a ketonic solvent such as methyl isobutyl ketone in combination with glacial acetic acid, acidified further with a mineral acid such as hydrochloric acid, provides a convenient acid medium for the detritylation.
As explained earlier, another key process step in the synthesis of TGS involves the chlorination of 4, 1' and 6'-positions of the sucrose pentaacetate. It is necessary to use a chlorinating reagent which will effect chlorination at all three positions. Insufficient chlorination leads not only to a low yield, but also to a product comprising a mixture of chlorinated derivatives, which is difficult to separate. Many well-known chlorinating reagents used in the carbohydrate field are insufficiently active to provide a good yield of the trichloro derivative and the usual methods involves the use of sulphuryl chloride. This chlorinating reagent is used in a mixture of an organic amine base, such as pyridine, and a chlorinated hydrocarbon, such as chloroform. The reaction proceeds by formation of chlorosulphate esters which are then decomposed to form chloro derivatives. The method used by Fairclough et al., (op.cit.) involves the use of a small excess of sulphuryl chloride to ensure complete chlorination and a low temperature, e.g. -75° C. rising eventually to room temperature. We have now found that a greater excess of sulphuryl chloride (e.g. 2-5 ml per 1 g of sucrose pentaacetate as opposed to about 1 ml per 1 ml of pentaacetate) and a much higher reaction temperature (e.g. 20 up to about 55° C. or more) gives improved yields, typically about 75%.
According to a further feature of the present invention, there is provided a process for the production of TGS, as defined above, further characterised in that the chlorination step (b) is effected using 2 to 5 ml of sulphuryl chloride per 1 g of sucrose pentaacetate at a reaction temperature of from 20°-80° C.
However, one disadvantage of this process is the fact that the organic amine, especially pyridine, tends to be chlorinated by the sulphuryl chloride, leading to the formation of unwanted by-products which are difficult to separate. We have now found that certain other chlorinating reagents, which would not be expected to give the desired product, can in fact be used to give high yields in a simpler reaction procedure.
A class of chlorinating reagents derived from triarylphosphines and carbon tetrachloride is known in the art for chlorinating carbohydrates Usually, the reagent is used under relatively mild conditions in order to obtain selective chlorination of the more reactive primary hydroxy groups only. Thus, when one molar equivalent of the hydroxy compound is reacted with three molar equivalents of triphenylphosphine and 1.5 molar equivalents of carbon tetrachloride in pyridine at 0° C., sucrose yields 6,6'-dichloro-6,6'-dideoxysucrose; while uridine, methyl-α-D-glucopyranoside, inosine and other similar carbohydrates give chlorinated derivatives in which the primary hydroxy group has been replaced by a chlorine atom selectively (Kashem et al., Carbohydrate Research 61 (1978) 511-518). A reaction procedure of this type is the normal way in which the reagent is used and the reagent is generally regarded as a selective chlorinating agent for more reactive primary positions. Under more forcing conditions, i.e. more of the chlorinating agent and higher temperatures, sucrose is still not chlorinated at both of the 1'- and 4-positions together, but instead appears to be degraded.
A variation of the reagent is reported by Regen & Lee (J.Org.Chem. 40 1669-1670, 1975). In this case, one of the aryl substituents on the phosphine molecule is replaced by a styrene group of a cross-linked polystyrene. The reagent thus becomes, in effect, a resin-bound triarylphosphine, which behaves in the same way as an ordinary triarylphosphine. The great advantage of the "immobilized" reagent is that it can be easily removed from the reaction material (either unreacted or in the form of the triarylphosphine oxide by-product) and the by-product can be regenerated.
We have now found that a primary chlorinating reagent of the triarylphosphine/carbon tetrachloride type can be used to chlorinate 2,3,6,3',4'-penta-O-acetyl sucrose in the process for preparing TGS under conditions which would be expected to chlorinate the more reactive primary hydroxy groups only. Most surprisingly, the 1'-primary hydroxy group is replaced by a chlorine atom, unlike the 1'-hydroxy group in sucrose itself which does not react with this reagent, and the secondary 4-hydroxy group is also replaced by a chlorine atom, as is the 6'-hydroxy group.
According to a further feature of the present invention, the process according to the invention for the production of TGS as defined above is further characterised in that in step (b) the pentaacetate is reacted with a phosphine derivative of the general formula P R1 R2 R3 (I)
(where R1 and R2 represent aryl groups; and R3 represents an aryl group or a resin-bound aryl group) in association with carbon tetrachloride, in an organic amine base, and at a temperature of from ambient to the reflux temperature of the system, preferably at a ratio of about 2 molar equivalents of phosphine derivative to 1 molar equivalent of carbon tetrachloride and preferably using at least 6 molar equivalent of phosphine derivative per molar equivalent of sucrose pentaacetate.
The phosphine derivatives may be divided into two types:
(a) those of Formula (I) in which R1, R2 and R3 are all aryl groups, such as phenyl or alkylphenyl groups;
(b) those of Formula (I) in which R1 and R2 are as described for (a), while R3 represents an aryl group bound to a resin, such as a phenyl group linked to a polymeric hydrocarbon, e.g. a phenyl group of a polystyrene resin.
A reagent of type (b) is described by Regen and Lee op.cit, namely polystyryldiphenylphosphine. This reagent may be regarded as triphenylphosphine bound by one phenyl group to a resin, or alternatively as a polystyrene resin of which a proportion of the phenyl groups are substituted with diphenylphosphino groups. This, and triphenylphosphine itself, are the reagents of choice.
The organic amine base is preferably a tertiary amine, especially a heterocyclic tertiary amine such as pyridine. In general, when using a ratio of 2 moles of phosphine derivative per mole of carbon tetrachloride in a base such as pyridine, the conditions are those which are well known in the prior art for selective chlorination at primary centres. Indeed, when these conditions are used on sucrose itself, only the 6- and 6'-positions are chlorinated. We have found, surprisingly, that at a temperature of from ambient to the reflux temperature of the system, this reagent will chlorinate at all three available centres of the sucrose pentaester, including the less accessible 1'-position and the secondary 4-position. The product is obtained in good yield and is substantially free of other chlorinated derivatives.
The reaction mixture may conveniently be worked up by adding a lower alkanol, such as methanol, to the reaction mixture and then evaporating the reaction mixture to dryness. The residue is then recrystallized from a suitable solvent after being washed with acid to remove basic materials. Where the phosphine derivative is resin-bound, the unreacted starting material and the phosphine oxide by-product can be removed simply by filtering the reaction mixture.
Another class of chlorinating agents which can be used in step (b) of the process of the present invention comprises the N,N-dialkyl(chloromethaniminium) chlorides of the general formula [XClCN+ R2 ] Cl- (II)
(where R represents an alkyl group, typically a methyl or ethyl group, and X represents a hydrogen atom or a methyl group).
Reagents of this type are prepared by reaction of an inorganic acid chloride with an N,N-dialkylformamide or N,N-dialkylacetamide. The inorganic acid chloride may typically be phosphorus pentachloride, phosgene, or thionyl chloride.
It is particularly surprising that this reagent will safely chlorinate in the 4,1'- and 6'-positions of a sucrose molecule as this class of acidic reagent is in general well known for its specificity as a chlorinator of more active primary hydroxy compounds. Thus, e.g. when N,N-dimethyl(chloromethaniminium) chloride was reacted with uridine, 5-chloro-uridine was obtained with no apparent chlorination in the two possible secondary positions (Dods & Roth, Tetrahedron Letters 165-168, 1969). Furthermore, reaction of a saccharide in which the primary hydroxy group and three of the four available secondary hydroxy groups had been protected by acetal formation to leave one free secondary hydroxy group yielded, in fact, a chlorinated product in which the primary hydroxy group had been replaced by chlorine, the protecting acetal having shifted to the secondary position. More specifically, 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose gave 6-chloro-6- deoxy-1,2:3,5-di-O-isopropylidene-α-D-glucofuranose in a yield exceeding 70% (Hanessian and Plessas, J.Org.Chem.34, 2163-2170, 1969).
We have now found that the reagents in question can be reacted with 2,3,6,3',4'-penta-O-acetylsucrose to give the corresponding trichloro derivative (i.e. TGS pentaacetate) in yields of well over 80%.
According to a further feature of the present invention, the process according to the invention for the production of TGS as defined above, is further characterised in that in step (b) the pentaacetate is reacted with a reagent of the formula [XClCN+ R2 ] Cl- (II)
(where X represents a hydrogen atom or methyl group and R represents an alkyl group), formed by reaction of an inorganic acid chloride with an N,N-dialkylamide of the formula R2 NCOX
(where X and R are as defined above).
The reaction is preferably effected with a small excess of the chlorinating reagent (e.g. about 4 moles of reagent per mole of sucrose penta-ester) in an inert solvent. The inert solvent may be, for example, a chlorinated hydrocarbon such as 1,2,2-trichloroethane or an aromatic hydrocarbon solvent such as toluene. The reaction is conveniently effected under reflux and preferably under a nitrogen atmosphere to maintain dry reaction conditions. The reaction mixture can be very simply worked up by evaporation to dryness and recrystallization from a solvent such as ethanol, desirably with a colour-removal step, such as a filtration through charcoal.
The reagent of formula (II) is conveniently formed in situ in the reaction vessel by direct contact of the inorganic acid chloride with the amide. Alternatively, the reagent may be formed beforehand and added as such to the reaction vessel. Formation of the reagent may be achieved by reaction of the acid chloride, e.g. phosphorus pentachloride or thionyl chloride, with the amide, conveniently either in approximately stoichiometric amounts or using an excess of the amide as solvent. Alternatively, since the amide is regenerated during the chlorination reaction, it is possible to use the required amount of the acid chloride and a "catalytic" amount of the amide, so that the chlorinating reagent is constantly being re-formed during the reaction.
This chlorination process thus provides a simple, rapid and easily worked-up reaction giving high yields of the desired chlorinated sucrose ester.
Yet another class of chlorinating agents of use in step (b) of the process of the present invention comprises the tri-substituted dichlorophosphoranes which can give high yields of product, often at ordinary room temperatures, in a selective and rapid manner.
According to a yet further feature of the present invention, the process according to the invention for the production of TGS by the method described above is further characterised in that the pentaacetate is reacted with a dichlorophosphorane derivative of the general formula Y3 PCl2 (III)
(in which Y represents an aryl group, e.g. a substituted or unsubstituted phenyl group especially an unsubstituted phenyl group, or an aryloxy group, e.g. a substituted or unsubstituted phenoxy group, especially an unsubstituted phenoxy group).
Reagents of the formula (III) in which Y represents an aryloxy group, may be prepared by reaction of a triaryl phosphite of the general formula Y3 P (where Y is an aryloxy group) with gaseous chlorine. This reaction can be effected simply by bubbling the chlorine gas into the liquid triaryl phosphite. Alternatively, the gas may be bubbled into a solution of the triaryl phosphite in an inert solvent. Reagents of the formula (III) in which Y represents an aryl group may similarly be prepared by reaction of a triarylphosphine of the general formula Y3 P (where Y is an aryl group), with chlorine gas. In this case, however, a solvent for the triarylphosphine is desirable, for example a chlorinated hydrocarbon such as carbon tetrachloride, which can subsequently be evaporated off before the reagent is used.
Triaryloxydichlorophosphoranes are a known class of compounds. Thus, for example, triphenoxydichlorophosphorane has been given the CAS Registry number 15493-07-9 by Chemical Abstracts and was reported by Coe et al. (J.Chem.Soc.1954 p 2281) to be a good chlorinating reagent for alcohols. However, this compound has been reported (Osake Kogyo Gijutsu Shikensho Kiho, 1967, 18, 117-122) to produce polymers when condensed with dihydroxy compounds. It is thus surprising that this class of reagent will safely chlorinate the three hydroxy groups of the above-mentioned sucrose pentaacetate.
Triaryldichlorophosphoranes are also a known class of compound. Triphenyldichlorophosphorane has the Chemical Abstracts CAS Registry Number 2526-64-9 and has been reported, for example by Wiley et al., J. Am.Chem.Soc 86, 964, (1964), as a chlorinating agent for alcohols. It has also been used for the cleavage of ethers and the chlorination of aldehydes and ketones and might thus be expected to be unsafe for the chlorination of sucrose derivatives.
The reagent of formula III is preferably formed immediately before use by chlorination of a triaryl phosphite or triarylphosphine as described above. The chlorination of the sugar ester is conveniently effected in a basic solvent, e.g. a tertiary amine such as pyridine. The reaction with a triaryloxydichlorophosphorane can conveniently be effected at ambient temperature or above e.g. 15°-60° C., possibly with cooling if necessary, since the reaction is mildly exothermic; the reaction with a triaryldichlorophosphorane, however, needs a higher temperature, e.g. from 50°-95° C.
The reaction mixture can conveniently be worked up by pouring it into water and extracting with an organic solvent such as dichloromethane. The extracts, when washed with acid and with base, dried and evaporated, yield a product which can be further purified by chromatography, for example on silica gel, to give a yield of the tri-chlorinated ester of approaching 80%.
The following examples illustrate the invention further. All temperatures are in degrees Celsius. Amberlite and Amberlyst are registered Trade Marks .
2,3,4,3',4'-penta-O-acetyl sucrose (2 g) was dissolved in methyl isobutyl ketone (20 ml) and acetic acid (1 ml) was added. The reaction of the mixture was heated under reflux (about 126°) for 3 hours. On cooling, the product crystallized to give a yield of 1.5 g (75%) of 2,3,6,3',4'-penta-O-acetyl sucrose.
2,3,4,3',4'-Penta-O-acetylsucrose (2 g; purity 83.63%) and glacial acetic acid (0.2 liter) were added to toluene (10.0 liter) and the mixture was heated to reflux and maintained at reflux for 6 hours or until the acetyl migration was completed. The solution was cooled to ambient temperature and the precipitate filtered off, washed with fresh toluene and dried in a vacuum oven at 40° C. to give 2,3,6,3',4'-penta-O-acetylsucrose (15.90 g; purity 87.65%) in an overall yield of 83.3%
Sucrose (100 g) and trityl chloride (270 g) were added to dry pyridine (600 ml) and stirred with heating at 65° for 18 hours. Pyridine was then removed under vacuum and the syrupy product was acetylated by the addition of acetic anhydride (600 ml) with stirring at room temperature for 12 hours. The reaction mixture was then poured into ice water with stirring and the precipitated product filtered off and dried to constant weight. A solution of this precipitate in dichloromethane (1 liter) was dried over sodium sulphate and concentrated to a syrup which was repeatedly dissolved in methanol, diluted with toluene and concentrated, to remove traces of pyridine. The product was then crystallised from acetone-methanol (1:9, 500 ml) at 0° to give 6,1',6'-tri-O- tritylsucrose penta-acetate (260 g, 70%).
6,1',6'-Tri-O-tritylsucrose penta-acetate (50 g) was dissolved in dichloromethane (500 ml) and acetic acid (500 ml) and the solution was cooled to 0° and concentrated hydrochloric acid (10 ml) was added thereto. The reaction mixture was stirred at 0° for 2 hours, and then neutralised by the addition of Amberlite IR 45 (OM) resin. The reaction mixture was stirred for 1 hour, concentrated to a syrup, and methanol (200 ml) was added. After 3 hours at 0°, the triphenylmethanol (27.6 g 96%) which had precipitated was filtered off and the solution was concentrated to a syrup. Acetone (400 ml) was added and the solution was decolorised with charcoal and then concentrated to a thin syrup. Ether (300 ml) was added and 2,3,4,3',4'-penta-O-acetylsucrose crystallised out at room temperature. (Yield: 20.5 g, 95%).
2,3,4,3',4'-Penta-O-acetylsucrose (20 g) was dissolved in methyl isobutyl ketone (200 ml) and acetic acid (10 ml) was added. The reaction mixture was heated under reflux at 125° for 2.75 hours. The reaction mixture was then cooled to 60° and petroleum ether (60°-80°) (200 ml) was added. On further cooling, 2,3,6,3',4'-penta-O-acetylsucrose crystallised out. After 16 hours at 0°, the crystalline product was filtered off, washed with diethyl ether and dried.
Yield=15.2 g (75%).
A solution of sulphuryl chloride (15 ml) in 1,2-dichloroethane (15 ml) was added to a solution of 2,3,6,3',4'-penta-O-acetylsucrose (5 g) in pyridine (15 ml) and 1,2-dichloroethane (15 ml) without external cooling. An exothermic reaction caused the temperature to increase to 45°-55°. The reaction mixture was heated under reflux for 4 hours, then cooled and dichloroethane (50 ml) was added. The resulting solution was washed successively with 10% hydrochloric acid (100 ml), water, and 10% sodium hydrogen carbonate solution to neutrality. The organic phase was dried, concentrated to a syrup and crystallised from toluene (25 ml) to give 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose penta-acetate.
Yield=4.1 g (75%).
4,1',6'-Trichloro-4,1',6'-trideoxygalactosucrose penta-acetate (20 g) was dissolved in methanol (200 ml), and I.O.N sodium methoxide in methanol was added until pH 9. The reaction mixture was stirred at room temperature for 4 hours, then neutralised with Amberlyst 15 (H+) ion exchange resin, filtered and concentrated to dryness. The solid product was dissolved in distilled water (60 ml) giving a cloudy solution which was filtered to give a clear colourless solution. The aqueous solution of TGS was then concentrated to dryness.
Yield=12.6 g (96%)
The overall yield from sucrose was 36%.
To a suspension of polymer-bound triphenylphosphine (Regen & Lee J.Org.Chem 40 (1975) 1669) (8 g, 6 molecular equivalents assuming approximately 80% substitution) in pyridine (38 ml) at 0° was added carbon tetrachloride (2 g, 3 molecular equivalents) followed by 2,3,6,3',4'-penta-O-acetyl sucrose (2.3 g, 1 molecular equivalent).
The mixture was then heated to 80° for four hours, cooled and filtered. The polymer beads were washed with dichloromethane and the combined filtrate and washings were evaporated to dryness. The residue was dissolved in dichloromethane and the solution was washed successively with 1 molar hydrochloric acid, saturated aqueous 1 molar hydrochloric acid, saturated aqueous sodium hydrogen carbonate and water and was then dried over sodium sulphate. The solution was then filtered through charcoal and evaporated to give 2.3 g of crude trichloro product. A crystallization of the crude product from ethanol gave 1.4 g (67%) of crystalline 4,1',6'-trichloro-4,1',6'-trideoxy-2,3,6,3',4'-penta-O-acetyl-galactosucro se. Further material was obtainable from the mother liquor.
To a solution of 2,3,6,3',4'-penta-O-acetyl-sucrose (4.9 g 1 molecular equivalent)in pyridine (100 ml) was added at 0°, triphenylphosphine (13.1 g 6 molecular equivalents),followed by carbon tetrachloride (3.9 g 3 molecular equivalents). The mixture was heated at about 70° for 3 hours and then cooled. Methanol (120 ml) was added to the cooled mixture, which was worked up by evaporating to dryness, dissolving the residue in methylene chloride, washing successively with 1 M HCl and NaHCO3 solutions, drying with Na2 SO4, filtering through charcoal and finally evaporating again to give a syrup. Acetone was added to the residue and any undissolved material was filtered off. The solution was again evaporated and the residue crystallized from ether. These crystals contained no sugary material and were discarded, while the solution was evaporated and then crystallized from ether/petrol to give 3.4 g(60%) of trichlorosucrose pentaacetate, slightly contaminatd with triphenylphosphine oxide. Recrystallization gave the pure product (2.3 g, 40%).
2,3,6,3',4'-Penta-O-Acetate From Reagent Derived From PCl5 and Dimethylformamide
Phosphorus pentachloride (50 g, 0.24 mole) was added in small portions to DMF (140 g, 1.92 moles) with stirring, during which the temperature rose to about 120° C. The mixture was then cooled to 0° C. and the N, N-dimethyl-chloromethaniminium chloride crystallised out and was filtered off. (See Hepburn and Hudson, J. C. S. Perkin 1, 754, 1976). To 1,1,2-trichloroethane (120 ml) was added N,N-dimethyl-chloromethaniminium) chloride (14 g, 4 molecular equivalents). This mixture was cooled to 0° C., and 2,3,6,3',4'-penta-O-acetylsucrose (15 g, 1 molecular equivalent) was then added, and the combined mixture was stirred and refluxed under nitrogen for 4 hours and then allowed to cool. The cooled reaction mixture was filtered through a charcoal pad, which was then washed with dichloromethane. The combined filtrate and washings were then evaporated to dryness and the residue was recrystallized from ethanol to give 13.45 g (82%) of the trichloro pentaacetate
Derived From Thionyl Chloride and DMF
Thionyl chloride (8.5 ml) was added to DMF (8.4 ml) which became hot and the mixture was evaporated under vacuum at 50° to give a syrup. To this was then added 1,1,2-trichloro-ethane (120 ml) and the mixture was cooled to 0°. Sucrose 2,3,6,3',4'-pentaacetate (15 g) was added and this mixture was refluxed for 3 hours, cooled and filtered through charcoal and the red-brown filtrate was evaporated to dryness. The resulting syrup was crystallized from ethanol to give 11.8 g (72%) of slightly coloured crystals. A recrystallization then gave 10.9 g (70%) of almost colourless crystalline trichloro -sucrose pentaacetate.
Pentaacetate Using a Vilsmeier Reagent Formed in Situ.
2,3,6,3',6'-Penta-O-acetylsucrose (5 g, purity 80%) was dissolved in a mixture of toluene (40 ml) and dimethylformamide (8.6 ml). A solution of thionyl chloride (8.3 ml) in toluene (15 ml) was added gradually to the stirred reaction mixture over a period of 15 minutes during which the temperature rose to 40° C. Upon completion of the addition, the mixture was stirred for a further 15 minutes and then heated to reflux and refluxed for 5 to 6 hours. The course of the reaction was monitored by thin layer chromatography. When the reaction was complete, charcoal was added and the warm mixture was stirred for 20 minutes and then filtered through a filter-pad. The residue remaining in the flask was washed with a little toluene which was also filtered. The combined filtrates and washings were evaporated and the residue crystallised from toluene (20 ml) to give 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose penta-acetate (4.32 g; priority 85.5%) in an overall yield of 84%.
Derived From Thionyl Chloride and a Catalytic Amount of DMF
To sucrose 2,3,6,3',4'-pentaacetate (2.75 g) in 1,1,2-trichloroethane (20 ml) was added DMF(approx. 0.15 ml) and the mixture brought to reflux. Thionyl chloride (1.7 ml) in 1,1,2-trichloroethane (10 ml) was added over approx. 45 minutes and the mixture refluxed for a further 5 hours. A further 0.15 ml DMF and 1 ml sulphuryl chloride was added at once to the mixture, which was refluxed for a further 3 hours.
The black reaction mixture was filtered through charcoal and the brown-red filtrate was evaporated to give a syrup which was crystallized from ethanol to give 6.3 g (40%) of trichloro sucrose pentaacetate as off-white crystals.
Chlorine gas was bubbled into triphenyl phosphite (3.1 g, 2.6 ml, 4 molar equivalents) (supplied by Aldrich Chemical Co.Ltd.) with stirring until a weight increase of 0.7 g was observed. The liquid became quite hot during the addition of chlorine and solidified on cooling. The cooled material was dissolved in pyridine (20 ml) and the sucrose 2,3,6,3',4'-pentaacetate (1.4 g, 1 molar equivalent) was added and dissolved. A crystalline precipitate formed almost immediately and, the mixture became quite warm. After 10 minutes, a sample showed on t.l.c. (ether/petrol) a single major product (Rf 0.5) corresponding to the pentaacetate of TGS together with two minor components (Rf 0.3 and 0.0). The mixture was stirred for a further hour and then poured into water and extracted with dichloromethane. The extract was washed with 0.1 N HCl and with sodium hydrogen carbonate solution and then dried (sodium sulphate), filtered through charcoal and evaporated to give a pale yellow syrup. This syrup was chromatographed on a column of silica gel, eluted with diethyl ether/40°-60° petroleum ether (4:1), to give TGS pentaacetate (1.2 g 78%) which was crystallized from ethanol and found to be identical with an authentic sample.
Chlorine gas was bubbled into a solution of triphenylphosphine (5.6 g) 8 ME) in carbon tetrachloride (20 ml) at 0° with stirring until a weight increase of 1.4 g was observed. Care was taken not to let the inlet tube get blocked with the reagent that was formed during the reaction. Some external cooling was applied as the reaction mixture became quite hot. The remaining solvent was evaporated and the residue dissolved in pyridine (10 ml). Sucrose pentaacetate (1.4 g, 1 ME) was added to this stirred solution and it dissolved with slight evolution of heat. The solution was left at room temperature for 21/2 hours and then was heated to 55° for 2 hours and then 85° for 3 hours, by which time the mixture had become very dark. T.l.c. analysis (ether/petrol 4:1) now indicated that a single compound (Rf 0.5) was present corresponding to TGS pentaacetate. The pyridine was evaporated and the residue was dissolved in dichloromethane and washed with 0.1 N HCl, and NaHCO3 solution, then dried (sodium sulphate), filtered through a charcoal pad to give a colourless filtrate and evaporated to give 6.5 g of a syrup. This was chromatographed as in Example 8 to give 1.1 g TGS pentaacetate, which crystallized from ethanol in 75% yield.


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OUR starter package.
a Do-It-Yourself guide to setting up a live escape game.
However unlike majority of the market, we do not just send you the files and expect you to build it with no assistance. Remote support is always available until the room is at a standard that meets your expectations.
the starter package includes:
Detailed blueprints of the game based on the room floor-plans.
Concept images for room design and images of our existing rooms.
Video walk through of the game.
List of items for building the game.
Digital puzzle files.
Clue delivery file with guidance on delivery.
Guides for building electronic puzzles - videos available if required.
Key points for brief and de-brief.
Permission to use game related video content.


text:
HULU 's FUTURE MAN VFX
My friends from ZOIC, called on me to design a logo and create a super fun animation sequence for the introduction of the "Die-Cathalon games," which appears in the climatic season two finale of Hulu's FUTURE MAN.
Think 80's themed olympics with killing…. Like the classic 1987 Arnold movie, "The Running Man". The sequence was executed to perfection by both NYC and LA office of the ZOIC team, and it was awesome to design for and work with such talents.
STILLS from the FINAL Animation by ZOIC.
Watch Season Two of FUTURE MAN on HULU to see the sequence.
Original concept boards for the awarded direction:
HULU's FUTUREMAN : VFX
Client : ZOIC
VFX Supervisor : Rocco Passionino
Producer : Shalena Oxley-Butler
VFX Coordinator : Amy Wascher
Design : Greg Herman


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When it comes to Halloween, we think of the two "C's" : Candy and costumes.
There are many other spooky ways to make the most out of your Halloween experience.
Here are some of our favorites:
Get in the mood
Some Halloween gurus keep a collection of scary movies just for this very purpose!
Go modern horror by watching The Witch (2016) that actually goes back to the days of the Salem witch trials. Witches do not disappoint when it comes to getting into the Halloween spirit.
Turn back the dial to the 1970s with the likes of Eraserhead (1977), Invasion of the Body Snatchers (1978) or even to the extreme with The Exorcist (1973).
Like Zombies? Shaun of the Dead (2004) is a solid horror comedy movie that will make you laugh and maybe jump out of your seat at the same time.
For your sweet tooth
We all love hot chocolate after an outing on a cold winter day, but adding spider toppers to your mug? That's just creepy (but delicious)!
Halloween doesn't have to be scary, gross or dark… You can be fancy too! This creepy Shirley Temple recipe is a good example of a popular classy drink gone spooky.
Next, we turn to desserts and sweets. You can't go wrong with a spider trifle cake recipe. Or you can even turn brie into a Halloween-themed snack with the "Mummy Brie."
Last but not least, you can enjoy some amazing Harry Potter recipes for an unforgettable Halloween.
Out of the house!
Montreal hosts a zombie walk, an organized get together where plenty of fans dress up as zombies and slowly walk around the streets… In (somewhat) orderly fashion!
Venture out to L'Ile Perrôt where you'll find Verger Labonté for thrilling corn maze experience. Prepare to get spooked!
For that thrill and suspense fix this Halloween, La Ronde hosts a Fright Fest, or if you want to sit and relax (but still be frightened), opt for Rocky Horror Montreal, an on-stage show that includes audience participation… Be prepared!
Looking for last minute ideas?
No problem! If there aren't any costumes left in store, you can still be last minute and come up with some impressive ideas.
We like clever: Check out this "Chip on your Shoulder" or "Copycat" costume amongst others for quick, easy and effective play-on-word options.
A group of guys each with a suit can be anything from Men in Black, security authorities, or anything else. If you have a fanny pack, a shoulder bag or backpack, a pair of shorts and a t-shirt, or other typical travel accessories, go ahead and dress up as a tourist!
Q: How do you make the most of your Halloween?