text:
Surrey is actually one of the best areas I've lived in, which is quite sad considering the comparisons to the US system.oakley half jacket 2.0 frame accessory kit 93965 LEGAL STUFF This is an unofficial site, and is not affiliated in any way with Universal Motown, Hip O Select or any of the artists referred to in the blog. Filed Under: Uncategorized Kelly Kitty September 10, 2015 by admin There Are More Pictures of Teen Redhead Here.ray ban clubmaster 51 black jets
04 Add to Basket Quick View Compare Product 14% Off Next Day Best Buy PowerBlock Kettleblock Stand (Double) List Price £174. { 0 comments } RUN paints Tramshed 26 Oct '12 RUN and Street Art London were recently invited to paint the front doors of Tramshed, Mark Hix's new restaurant in Shoreditch, notable for its commissioned Damien Hirst piece inside featuring a cow and a cockerel.ray ban 3025 blue gradient nails Patrick CostumesWorld Country CostumesLetter 'L' CostumesTagsst patricksleprechaunQ & AQ & AHave a question about this product.
Suzy uses her trusty dildo to fill her tight pussy passage and it just doesn't seem to get her off so she calls in the help of Sophie to help her get that delectable pussy off and Sophie can never say no to Suzy since that sweet pussy tastes like candy. Netherlands Amsterdam Enschede Zwolle Germany Dusseldorf Frankfurt Munich France Paris Switzerland Geneva Zurich UK London UAE Dubai Asia Data Centres.ray ban round sunglasses copy of All the energy you take into the planning and prep work will be paid back by delighted, amused children and unwinded, engaged grownups.
Again, whether you fully believe Donaghy or not, he does provide a fascinating perspective into the world of refereeing that simply no one else can provide.


text:
Illustration • Submitted
0 ratings· 1 view
Adam Pengilly was selected to represent his home nation of Great Britain during the 2010 Winter Olympics in Vancouver. At one time, Pengilly, was a bobsledder, but decided to change over to the more challenging sport of riding a skeleton sled. He told a reporter, "The first run that you ever take is…

subset: commoncrawl


text: Filter News By category (Coventry) All Press Releases Fundraising News By date All May 2017 April 2017 March 2017 February 2017 January 2017 December 2016 November 2016 October 2016 September 2016 August 2016 July 2016 June 2016 April 2016 February 2016 January 2016 November 2013 News - Latest Royal Message of Support for Children's Hospice Week 22/05/2017 Royal message of support from HRH The Duchess of Cambridge Read more Let's turn up the volume on Children's Hospice Week! 22/05/2017 Join Zoë's Place Baby Hospice and UK charity Together for Short Lives for this year's Children's Hospice Week (22-28 May). The campaign will be turning up the volume on children's palliative care to raise awareness about the needs of seriously ill children and to celebrate lifeline services that children and... Read more Challenge Q&A with our "Bearded Adventurer"! 05/05/2017 YES! It's "Feel Good Friday" and time to feature another of our amazing challengers! This time we thought we would do it Q&A Style……… This week's focus is on the Amazing Mr. Rigley, mountain climber and mud run challenger extraordinaire! Q&A Session: Q: Tell us about Trevor Rigley... Read more Graham gets just Desert As a challenge events fundraiser I have supported many a crazy challenger over the years, but I believe that Graham Black's challenge takes some beating! This is because this weekend Graham is taking on the infamous Marathon de Sable, and if you haven't heard of it, you are probably quite sensible! To complete his challenge Graham will run over 250km (156 miles) over 6 days, through endless dunes and across white-hot salt plains. Read more One pensioner, One bike, One Tour d'Italia! What are your plans this weekend? A... Read more Meet Rich, our Challenge Events Super Hero! We are so lucky here at Zoë's... Read more ITV to feature Zoë's Place Coventry! This year marks the 50th anniversary of the... Read more Switch on, Tune in! We are thrilled to be part of Radio Plus... Read more Christmas Fayre Success! A huge congratulations to everyone who... Read more


text:
Tim Holtz fabric, 108 in. wide, Correspondence TaupeCode: QBTH001
Price: $6.75
Tim Holtz fabric, 108 in. wide, Correspondence TaupeCode: QBTH001
Regular Price:
Sale Price: $6.75
Product Details
Priced and sold per 1/2 yard. This Eclectic Elements-Tim Holtz fabric is 108 in. wide, 100% Cotton Sateen Chintz. The perfect backing fabric to finish any quilt, beautiful as curtains, dust ruffles, tablecloths or in any home décor project. This large-scale soft cotton perfect complements any of the Tim Holtz collections, while also standing on its own as something new and different. For scale, the October French postmark graphic pictured here is approximately 4.5 in. across.


text:
Digital Marketing Megatrends 2017
Learn the 5 pillars of multichannel marketing and 9 actionable trendsFREE DOWNLOAD
Your product or services will likely solve a problem for your customers, or fulfil particular needs and wants. No matter how boring you view this product, it sits within a 'story arc' that can always be made interesting to consumers facing the challenges that it solves.
In Joseph Campbell's book The Hero with a Thousand Faces, a basic pattern of storytelling is defined as a 'monomyth' or 'hero's journey'. This is a pattern that can be seen in a wide range of storytelling from around the world. Essentially, protagonists within a story go through a number of common stages, as below:
From Homer's The Odyssey, to Medieval Romances and modern sci-fi adventures such as Star Wars Episode IV: A New Hope and Avatar, this story arc persists:
Using Star Wars as an example, the story arc is easily recognisable:
We can use this kind of story arc in a content marketing strategy through switching the protagonist with the customer, and then offer mentorship through the content, and the promise of reward (or quest completion) from the product. For instance:
While the second story is hardly going to make audiences as excited as one of the most successful films of all time, it can help you shape a relevant structure for you content marketing plan. For instance, from Joe's potential 'quest', you could shape it as follows:
This story arc has a good understanding of the protagonist (who could be defined by your personas), their challenges and how you could solve these. It's a great place to start from!
By James Carson
James Carson is a Content Strategy consultant and owner of Carson Content. He was formerly Head of Digital Marketing at Bauer Media, where he oversaw digital integration and content strategy for some of the UK's largest media brands including FHM, Grazia and heat. You can talk to him on Twitter, Google+ or LinkedIn.
Start the discussion on our community and social networks
Recommended Blog Posts
What is headless CMS and how can it benefit marketers? It's a question that you may have either been asked or have asked yourself in the last few months—"what exactly is headless CMS and why should marketers care?" It's unproven. It's …..
Popular Blog Posts
Statistics on consumer mobile usage and adoption to inform your mobile marketing strategy mobile site design and app development "Mobile to overtake fixed Internet access by 2014" was the huge headline summarising the bold prediction from 2008 by Mary Meeker, an …..
Landing page examples and best practice advice Discussion of web design in companies who don't know the power of landing pages still often focuses on the home page. But savvy companies know that custom landing pages are essential to maximise conversion …..
Use the RACE Planning System to get ahead in your digital marketing The first edition of my book Internet Marketing: Strategy, Planning and Implementation from 2001 included a popular template for creating what we then called an Internet Marketing Plan. Today, …..


text: BMW R80RT (1991/K) £3,150 798cc20,921 milesLancashire Red BMW R80RT, mono shock, very low mileage, MOT history to confirm mileage. MOT Certificate till 18th May 2018. Previous owners 2, excluding current. Nice clean BMW, well maintained and garaged. Everything is in working order. Age related marks as... Private Seller +5 Photos Theft Checked Get a full history checkHPI check Get an insurance quoteInsurance quote View details


text:
RTU 2016 3rd Sem Main Back B.Tech Result : hello friends welcome to our website today in here we are availing you the RTU 2016 3rd Sem Result which most of you are searching for. The Rajasthan Technical University soon going to declare the RTU 3rd Semester Result for 2015-16 session, The candidates who had […]
Recent Answer keys
- 17 Jan SSC Junior Hindi Translator Answer Key 2016 ssconline.nic.in exam Solution
- Download IRCON Works Engineer Asked questions/Cut Off Marks / Result 2015
- UPSC CAPF AC Asst Commandants expected cutoff 2016 by category | merit list
- Today UPPSC Lower Subordinate mains answer key 2016 – UPPCS Paper-I, II uppsc.up.nic.in
- AMUPMDC ASSO CET Expected cutoff, Merit List & Result 2015 Answer Key Sheet PDF
- Gujarat Police PSI ASI Constable 2nd 3rd 4th May Answer Sheet 2015 – Solved Keys
- RRB JE 30A ug Ques. Paper with Answer key 2015 | RRB JE Key
- Updated WBSSC TET cutoff / merit list / result 2015 – West Bengal SSC
- Today GSEB HSC SEM 4 Physics Answer key 08/03/2016 pdf
- cut off rrb chennai sse 2015 – secunderabad, bangalore


text:
On Blogger since November 2009
Profile views - 160
My blogs
Blogs I follow
- Crazy For Cloth Diapers!!
- DewingJones
- Family of the Cloth
- Going Peanuts: A Young Mom's Tale
- Granola Mom 4 God
- Happy Baby Bunz
- Maxwell Designs Blog
- realdiaperevents.org
- Stockpiling Moms
- The Crunchy Wife
- Truth Be Told
- Turning the Clock Back
|Originally from a small farm town in Indiana, I am currently working part-time as a certified guidance counselor in the greater Cincinnati area. I am a Christian, the wife of my best friend and the mother of an amazing daughter that keeps us all on our toes!
|Cooking, gardening, reading, dancing, music, friends!


text:
Maple Sugaring
Spring Hours
Building: Wednesday - Sunday 9:00 am to 5:00 pm
*Building closed Mondays & Tuesdays
Trails: Dawn to Dusk Daily
Summer Hours
Building: 7/7 9:00 am-5:00 pm June 15 through Labor Day
Stay in Touch
8023 State Route 30 Paul Smiths, New York 12970
Contact Us»
Stick with us!
The Paul Smith's College VIC is proud to participate in maple sugaring education at our demonstration sugaring operation. Join us for FREE interpretive programming, or just stop by during NYS Maple Weekends to get a taste of our VIC-made syrup! You can also support VIC maple educational programming through our Adopt a Maple program!
Adopt a Maple!
Support the development of maple sugaring at the VIC by adopting a Sugar Maple tree for $50. We'll do the tapping, and you'll be investing in the VIC's maple programming and the equipment to take loving care of the tree. The best part is you get a quart of maple syrup from "your tree" when it's ready! (plus the cost of shipping). Adoption papers are available at the VIC front desk or you can find them by clicking here. Makes a great gift!
NYS Maple Weekends
Dates: Saturdays and Sundays, March 18,19 & 25,26
Time: 10:00 am – 4:00 pm
Who: All ages!
Cost: Free
More details: The VIC is proud to be a part of New York State Maple Weekends. Stop by and say hello to our sugar shack student workers, staff, and volunteers and taste the sweetness of maple syrup made at the VIC!
March Interpretive Maple Tours
Dates: Saturdays and Sundays through March
Time: 1:00 pm – 2:00 pm
Who: All ages
Cost: Suggested donation of $10 per person
More details: Bring your own snowshoes and join a VIC naturalist for a walk through the woods and to our sugar shack to learn about the art and science of maple sugaring!
History of Sugaring at the VIC
In 2013, the Paul Smith's College VIC collaborated with Cornell Maple and The Wild Center to expand maple syrup and sugaring opportunities in northern New York. The VIC developed two demonstration sugar bushes – one with lines and one with buckets – to model what a family could do in their own back yard.
In the VIC's first season, we used a mobile sugar shed set up near the VIC building, and in the fall of 2013, VIC staff, along with volunteers and Paul Smith's College students, built a new VIC Sugar House. The majority of the lumber was harvested from the VIC grounds, and some was milled on site by students using the college saw mill.
Maple products produced at the VIC are sold at Packbasket at the VIC, our on-site shop. The VIC offers interpretive programs, free for the public, on maple sugaring and participates in the NYS Maple Weekends. The maple project has also been integrated into the environmental education programs for school children as well as Paul Smith's College students, and interpretive signage is being developed for both the VIC Sugar House and the VIC Sugar Bush.
We also encourage VIC neighbors to participate in our community maple sugaring program. You collect the sap, and we process it to make beautiful sweet syrup. For more information, contact us!


text:
When it comes to being environmentally friendly, the enormous annual Christmas card tradition is more like an enemy. Christmas cards are printed up by the billions, using vast amounts of paper resources. After they are read by their recipient, they will often be tossed in the trash to head to the growing landfills. Many people these days are concerned about their effects on our environment. However, there is no need to give up the fun and heartwarming tradition. Instead, simply look for some ways of going green with green Christmas cards.
Mailing out Christmas cards to friends and loved ones is, to some people, as important a part of the holiday as the turkey is to Thanksgiving. It is probably not a tradition that they are willing to give up. Luckily, they do not have to let go of their holiday family traditions, which have been around since the 1800s. Going green with green Christmas cards can eliminate the environmental concerns, causing a win-win situation for everyone.
Sending E-cards is one of the most popular ways of going green with green Christmas cards. Everyone uses this technology daily. In fact, we have now all become so accustomed to it that it is likely we could not survive without it. Therefore, it may be a great idea to utilize the Internet to send out our Christmas cards. There are many programs online where one can design their own cards or select from from a variety of fun designs. The cards are sent out by email, completely eliminating the prospect of having any wasted paper.
Some people think that you just can't beat the physically delivered Christmas card on real paper. For those unwilling to switch over to technology-oriented mailing lists, it is simple to just get more involved in recycling. One can take all their used Christmas cards to a designated recycling facility so that the paper waste can have a second life. Numerous card sellers are also switching their materials over to completely recycled paper in order to have a lesser effect on the environment. These are all great ways of going green with green Christmas cards.


text:
CBS's New NFL Deal: Thursdays Just Got Interesting (and Maybe Mondays, Too)
Our theory about what it all means for The Big Bang TheoryBy Josef Adalian
Our theory about what it all means for The Big Bang TheoryBy Josef Adalian
Things Are Happy — a Little Too Happy — in the First Look at Pretty Little Liars' Series Finale
No One Is More Shocked Than Joaquin Phoenix That He Won Best Actor at Cannes
Male Stars Are Too Buff Now
The Saturday Night Live Season That Almost Was
Silicon Valley Recap: Richard Hendricks Gets Laid!
Classic Bass: Ed Westwick Wants Nothing to Do With a Gossip Girl Revival
David Lynch Forces Your Brain to Work Differently
The Leftovers Recap: Are You a Bad Enough Dude to Kill the President?
What Is Katy Perry Doing?
House of Cards' Fifth Season Is Bonkers, in a Good Way


text:
|Publication number
|Publication type
|Application number
|Publication date
|Jun 30, 1992
|Filing date
|Dec 7, 1990
|Priority date
|Dec 7, 1990
|Fee status
|Publication number
|Navzer D. Sachinvala
|Original Assignee
|Hawaiian Sugar Planters' Association
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Non-Patent Citations (10), Referenced by (3), Classifications (13), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
The present invention relates to a sucrose intermediate. More particularly, the present invention relates to sucrose intermediates having the structure: ##STR1## wherein X is selected from the group consisting of chlorine, bromine and iodine. In a preferred embodiment of the present invention, the compound of structure (I) is 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose and is useful as an intermediate in the synthesis of other difunctional monomers. Compound (I) may also be used as a monomer for the preparation of novel water-absorbent polyethers.
2. Description of the Prior Art
In the past, many attempts have been made to employ carbohydrates for the development of well-characterized novel polymers of some practical significance. The use of sugars and their derivatives in the production of polymers is of growing interest since polymers containing mono- or disaccharides in their main chain or as grafted pendant groups or chains display useful and unique properties such as hydrophilicity, chirality, biological activity, biodegradability, and the like. Furthermore, most sugars are available at economical prices and are industrially produced in large quantities by cultivation in plants and microorganisms, followed by chemical isolation or by degradation of plant waste material followed by isolation. For instance, sucrose is produced on a scale that is larger than any other pure organic chemical, world-wide.
The major problem associated with the use of carbohydrates for developing polymers is the similar reactivity of the primary and secondary hydroxyl groups on the carbohydrate moiety. Hence, when carbohydrates are polymerized non-enzymatically with other monomers, the resulting polymer products are often a mixture of linear, cross-linked and branched chain products. This is due to the reaction of both the primary and secondary hydroxyl groups in the carbohydrate moiety with electrophilic groups in the other monomer.
Many attempts have been made in the past towards polymerizing carbohydrates such as those attempts described by N. Ogata et al in J. Polym. Sci., Polym. Chem. Ed., Vol. 19, p. 2609 (1981) and Vol. 22, p. 739 (1984); and S. K. Dirlikov, "Monomers and Polymers Based on Mono and Disaccharides", Pacific Polymer Preprints, First Pacific Polymer Conference, Dec. 12-15, 1989, Volume 1, pp. 113-114.
Although Dirlikov, supra, claims that high molecular weight polymers have been made, no proof has been shown that these polymers are strictly linear and do not contain additional cross-linked or branched chain polymers and that only the primary hydroxyl groups react thereby forming a strictly linear polymer.
Sucrose used as a starting carbohydrate for the production of carbohydrate polymers would be ideal since it is produced in vast quantities and is low in price. To synthesize intermediate sucrose derivatives for further use in the production of novel polymers using sucrose as a starting compound is difficult due to the reactivity of the primary hydroxyl groups at carbons 6, 1' and 6' and the remaining five secondary hydroxyl groups.
Several sucrose derivatives used as intermediates in the preparation of a variety of products have been previously described. For instance, U.S. Pat. No. 4,117,224 relates to the preparation of 6,6'-dichloro-6,6'-dideoxysucrose and 1',6,6'-trichloro-1',6,6'-trideoxysucrose. These intermediates can be used in the preparation of the corresponding anhydro, azido and amino derivatives which can be used to make various resins.
Sweetening compounds of 4,1',6'-trichloro-4,1',6'-trideoxygalactosucrose are described in U.S.Pat. No. 4,612,373. The alkyl and ether derivatives are also described and these sucrose derivatives are about 400 times sweeter than sucrose.
Whistler et al in Methods in Carbohydrate Chemistry, VIII, 227 (1980) describes the synthesis of 6,6'-dichloro-6,6'dideoxysucrose. Although this is a known compound, it is difficult to use 6,6'-dichloro-6,6'-dideoxysucrose as an intermediate in the preparation of various methylated derivatives due to its structure. It is also not possible to use this compound as a monomer in the development of linear polyethers by Williamson ether synthesis.
It has now surprisingly been discovered that the compound of structure (I) wherein X is selected from the group consisting of chlorine, bromine and iodine and the preferred embodiment, namely 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose can be used as key intermediates in the preparation of other difunctional monomers, as well as monomers for preparing novel water-absorbent polyethers.
It is an object of the present invention to avoid or alleviate the problems of the prior art.
It is another object of the present invention to provide 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose, 6,6'-dibromo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose and 6,6'-diiodo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose, which can be used in the preparation of other difunctional monomers.
It is yet another object of the present invention to provide the aforementioned hexa-0-methylsucrose compounds for use in the synthesis of high molecular weight polyethers.
Basically, the present invention features compounds having the structure (I): ##STR2## wherein X is selected from the group consisting of chlorine, bromine, and iodine.
Another feature of the present invention is a method of using 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose as an electrophile to make a polyether with an alkyl or an aryl diol comprising generating a bisalkoxide from a bishydroxide by treatment of said bishydroxide with a non-nucleophilic base to form a bisalkoxide and reacting said bisalkoxide with said 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
Yet another feature of the present invention is a method of using 6,6'-dibromo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose as an electrophile to make a polyether with an alkyl or an aryl diol comprising generating a bisalkoxide from a bishydroxide by treatment of said bishydroxide with a non-nucleophilic base to form a bisalkoxide and reacting said bisalkoxide with said 6,6'-dibromo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
Still yet another feature of the present invention is a method of using 6,6'-diiodo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose as an electrophile to make a polyether with an alkyl or an aryl diol comprising generating a bisalkoxide from a bishydroxide by treatment of said bishydroxide with a non-nucleophilic base to form a bisalkoxide and reacting said bisalkoxide with said 6,6'-diiodo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
FIG. 1 represents the synthesis scheme of 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
FIG. 2 is an 1 H NMR spectrum of 1',6,6'-tri-O-tritylsucrose synthesized by the process of the present invention.
FIG. 3 is a 13 C NMR spectrum of 1',6,6'-tri-O-tritylsucrose synthesized by the process of the present invention.
FIG. 4 is an 1 H NMR spectrum of 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose synthesized by the process of the present invention.
FIG. 5 is a 13 C NMR spectrum of 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose synthesized by the process of the present invention.
FIG. 6 is an 1 H NMR spectrum of 2,3,3',4,4'-penta-O-methylsucrose synthesized by the process of the present invention. FIG. 7 is a 13 C NMR spectrum of 2,3,3',4,4'-penta-O-methylsucrose synthesized by the process of the present invention.
FIG. 8 is a 1 H NMR spectrum of 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
FIG. 9 is a 13 C NMR spectrum of 6,6'-dichloro-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose.
As described herein, the term "dihalo" means dichloro, dibromo or diiodo and does not include difluoro compounds. Similarly, the terms "dihalide" and "tetrahalomethane" do not include fluorine compounds.
More specifically, the synthesis of the compounds of structure (I) involves the selective manipulation of 2,3,3',4,4'-penta-O-methylsucrose in pyridine with triphenylphosphine and a compound selected from the group consisting of chlorine, bromine and iodine to generate the corresponding 6,6'-dihalo, 6,6'-dideoxy analog of penta-O-methylsucrose. The preparation of the dihalide containing either bromine, chlorine or iodine groups at the 6, 6'positions sets the stage for its nucleophilic displacement. However, this conversion cannot take place unless the 1'-hydroxyl group in the dihalo, dideoxy compound is blocked. By methylating the 1' oxygen the compounds of structure (I) are obtained.
The starting compound used in the synthesis of the compounds encompassing the structure of (I) is 2,3,3',4,4'-penta-O-methylsucrose. 2,3,3',4,4'-Penta-O-methylsucrose is synthesized from sucrose by converting sucrose to 1',6,6'-tri-O-tritylsucrose, which is converted to a penta-methyl ether moiety and reduced with an alkali metal in liquid ammonia to form the final product.
The starting compound, sucrose, is first converted to 1',6,6'-tri-O-tritylsucrose by reacting sucrose with trityl chloride. This method is described by Hough et al in the journal Carbohydrate Research, Vol. 21 (1972), pp. 414-417, and is incorporated herein with some modifications. Specifically, the process involves the addition of trityl (triphenylmethyl) moieties to the 1', 6, and 6' positions on the sucrose molecule. The synthesis is performed by adding a solution of trityl chloride in dimethylformamide to a solution of sucrose in dimethylformamide and triethylamine. The amount of sucrose used may vary. For instance, between 314 mg (1 mmol) to 70 grams (204.5 mmol) of sucrose may be used. The amount of trityl chloride may also vary depending on the amount of starting sucrose used. For instance, about 4.5 times the molar amount of trityl chloride is used per mole of sucrose, and, therefore, it is preferable to use 260 grams (935 mmol) of trityl chloride per 70 grams (204.5 mmol) of sucrose. After dropwise addition of a solution of trityl chloride in dimethylformamide at 0� to 5� C. over a time period of about one hour, the mixture is allowed to warm to room temperature and then stirred at a constant temperature of about 45� C. for two days. The mixture is then concentrated to about half the original volume under reduced pressure and dissolved in methylene chloride, washed successively with water, 1M hydrochloric acid, saturated aqueous sodium bicarbonate, water, and brine, and then dried in the presence of sodium sulfate. The methylene chloride is then removed in vacuo. The residue is then applied on a column of silica gel (230 to 400 mesh) and eluted successively with methylene chloride, 10% acetone in methylene chloride and 20% acetone in methylene chloride at a flow rate of about 100 ml/min. 100 ml fractions are collected, and each fraction is spotted on a thin-layer chromatography plate, and the plate is developed with 20% acetone in methylene chloride. Three compounds elute from the column with methylene chloride and 10% acetone in methylene chloride. These three compounds are nonpolar compounds and typically have Rf values of 0.83, 0.74, and 0.62 on silica gel 60 plates (0.25 mm, F-254 E. Merck). The desired 1',6,6'-tri-O-tritylsucrose elutes with 20% acetone in methylene chloride and has an Rf value of 0.21 in 20% acetone in methylene chloride. The yield of 1',6,6'-tri-O-tritylsucrose using this method is typically between 65% and 70%.
The tri-O-tritylsucrose adduct is then O-methylated at positions 2,3,3',4 and 4'to produce 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose. The penta-O-methylation is performed under conditions that take advantage of the fact that a hydride base reacts rapidly with the secondary alcohols to produce hydrogen gas and the said alkoxides, without the possibility of reverting back to the alcohols. The alkoxides are then alkylated with an alkylating agent such as methyl iodide or dimethyl sulfate to produce the penta-O-methyl ethers.
In the synthesis of the intermediate compound, 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose, all group (I) and group (II) metal hydrides, as well as all group (I) and group (II) bases can be used to convert the secondary alcohols to alkoxides. More specifically, sodium hydride, potassium hydride and the like. It is preferable to use sodium hydride.
Alternatively, lithium bases can also be used. In the case of alkyl lithium bases, a solution of the lithium base is added to the polyhydroxy compound at low temperatures. Specific examples include methyllithium, butyllithium, t-butyllithium, phenyllithium, sodium hydride, potassium hydride, and the like, to mention only a few.
The amount of group (I) and group (II) metal hydrides and the aforementioned bases utilized in the second step of this process may vary depending on the amount of 1',6,6'-tri-O-tritylsucrose used in the reaction. For scales up to 10 mmol or 10.69 grams of tri-O-tritylsucrose, approximately 6 grams to 10 grams or 150 mmol to 250 mmol of a 60% dispersion of sodium hydride in oil are used. The presence of 3 to 5 equivalents of hydride base per reactive hydroxyl group in tri-O-tritylsucrose will ensure complete deprotonation of the alcohol to form the alkoxide, without the possibility of reverting back to the alcohol, provided no excess proton source is purposely introduced into the reaction mixture (i.e., by addition of water or other protic solvents). The excess sodium hydride is added to assure that the reaction mixture stays dry in case traces of moisture are accidentally introduced. If greater than 10 mmol of 1',6,6'-tri-O-tritylsucrose is reacted, i.e., 50 grams (46.76 mmol) to 150 grams (140 mmol), then an equal weight in grams of sodium hydride (60% in oil) is used. Thus, for instance, for 150 grams of tri-O-tritylsucrose, 150 grams (3900 mmol) of sodium hydride (60% dispersion in oil) is used. For large scale synthesis, it is preferable to use 5 equivalent excess of hydride ion for each hydroxyl group in tri-O-tritylsucrose.
The hydride is usually stored as a dispersion in oil at varying concentrations. Prior to using the hydride base in the reaction, it should be washed free of the oil with pentane. Then the washed hydride is resuspended in a suitable solvent. Any polar aprotic solvent that can suspend or dissolve the hydride may be used, provided the solvent and hydride do not destructively react at the temperatures needed to deprotonate the alcohols. For example, dimethylformamide (DMF) begins to decompose in the presence of sodium hydride at 55� C. to 60� C. within a few hours to produce carbon monoxide and sodium dimethylamide. Examples of suitable hydrides and their corresponding solvent for this reaction include sodium hydride in DMSO, potassium hydride in DMSO at low temperatures of 0� to 40� C., sodium hydride in tetrahydrofuran (THF), potassium hydride in tetrahydrofuran (THF), sodium hydride in HMPA (hexamethylphosphoric triamide), sodium hydride in N-methylpyrrolidone, potassium hydride in N-methylpyrrolidone, sodium hydride in DMSO/THF, potassium hydride in DMSO/THF at low temperatures of 0� to 40� C., sodium or potassium hydrides in DMF at low temperatures of 0� to 40� C., calcium hydride in hexamethylphosphoric triamide, methyllithium, phenyllithium, butyllithium, sec-butyllithium or t-butyllithium in ether solvents such as tetrahydrofuran (THF), dioxane, dimethoxyoxyethane, diethylether or t-butylmethyl ether, alkyl lithium or aryl lithium and magnesium reagents in hexamethylphosphoric triamide or N-methylpyrrolidone, transition metal salts and hydrides of copper, cadmium, cobalt, and the like. It is preferable to use dimethylsulfoxide (DMSO) for a variety of reasons since methyl protons of DMSO are less acidic than the hydroxyl group protons of tri-O-tritylsucrose, DMSO does not completely react with sodium hydride to form the dimsylanion within 30 to 60 minutes at temperatures ranging between 25� C. to 55� C., and the red penta anion of tri-O-tritylsucrose is very soluble in DMSO. Moreover, since only small amounts of the dimsylanion is formed by using DMSO, the anion will react with the hydroxyl groups in tri-O-tritylsucrose to form alkoxides. The amount of solvent used in the present invention may vary depending upon the amount of tri-O-tritylsucrose and hydride used in the reaction. It is preferable to use 10 ml of DMSO per gram of tri-O-tritylsucrose or 0.1M tri-O-tritylsucrose in DMSO.
The addition of the 1',6,6'-tri-O-tritylsucrose to the hydride base usually takes place at a temperature between 45� C. to 55� C. to permit the formation of alkoxides. It is preferable, however, that the reaction proceed at a temperature of about 50� C. to 60� C., most preferably about 50.C. The internal temperatures do not ever rise above 60� C.
This addition usually takes place over a period of 20 minutes to three hours depending on the amount of starting 1',6,6'-tri-O-tritylsucrose being used. For instance, if up to 10 mmol of the tritylsucrose is being reacted, then the addition takes place over a period of about 30 minutes. If the starting tritylsucrose concentration is greater than 10 mmol, then the addition to the hydride base may take up to 3 hours. The 1',6,6'-tri-O-tritylsucrose is added dropwise under constant stirring while the reaction temperature is monitored by placing a thermometer in the stirring vessel. After the addition of the tritylsucrose, the reaction mixture is maintained at the above-described temperature and constantly stirred for an additional time period. Usually this period is approximately 90 minutes.
After hydrogen evolution has ceased completely, a burgundy-red solution is obtained. This solution is then cooled to a temperature between 0� C. and 25� C.
Upon cooling the reaction mixture, an alkylating agent is then added dropwise over a varying time period, depending on the amounts of alkylating agents being added. For instance, in preparation containing up to 10 mmol of the tritylsucrose, the alkylating agent may be added over a period of about 30 minutes since less of the alkylating agent is used in the reaction. For preparations of larger than 10 mmol, the alkylating agent may be added over a time span of up to 90 minutes.
Any alkylating agent may be used in the present invention that will add on alkyl moiety to the alkoxide. Examples of the alkylating agents, which may be used in the present invention include methyl iodide, dimethyl sulfate, methyl chloride, methyl bromide, benzyl bromide, allyl bromide, octyl iodide, butyl iodide, halides and sulfonate esters of long chain hydrocarbons, and the like. If methyl iodide is used in this method, then it is usually freshly distilled over copper. The concentration of the alkylating agent may vary depending upon the amount of starting material present in the reaction medium. It is preferable to use a 5 molar equivalent excess of alkylating agent for each hydroxyl group in tri-O-tritylsucrose. Thus, for example, if 100 mmol of tri-O-tritylsucrose is used, 500 mmol of hydroxyl groups/100 mmol tri-O-tritylsucrose react and therefore 2,500 mmol of alkylating agent is used.
The alkylating agent is added over a period of time at a variety of temperatures, which depend upon the alkylating agent used. For instance, if methyl iodide is used, the reaction should be cooled to 0� C. and should not rise above 10� C. during the reaction. The addition of said alkylating agent should be very slow to preclude the internal temperature of the reaction from rising to the boiling point since the alkylating agent may evaporate. The reaction is then stirred at room temperature for a period between 2 to 24 hours. At this point, the mixture can be concentrated to one-fifth the volume at a temperature of about 60� C. under 0.1 mm Hg, if desired. Then the solution or concentrated solution is treated with a 10% solution of sodium hydroxide and stirred for an additional time period. After the addition of the sodium hydroxide, the resulting mixture is then diluted with water and an extracting agent such as methylene chloride or ethyl acetate. The extraction with the solvents is usually repeated at least twice, and the organic extracts are combined and further washed with water and brine. The washed organic extracts are then further dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to provide a residue.
The residue is then placed over a silica gel column and the final product is eluted therefrom with a 1:1 hexane:methylene chloride solution of approximately 2 liters; followed by methylene chloride and 5% ethyl acetate in methylene chloride. The flow rate of the column varied between 100 ml/min to 200 ml/min.
The yield of 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose obtained by the above process is between 89% to 97%.
The 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose obtained is converted to 2,3,3',4,4'-penta-O-methylsucrose by unmasking the tri-O-trityl protecting groups to regenerate the hydroxyl groups at positions 1',6 and 6'. The trityl groups are removed by reduction without adversely effecting the glycosidic linkage. This reductive cleavage is performed by using alkali metals in the presence of liquid ammonia in a suitable aprotic solvent such as tetrahydrofuran (THF). Alternatively, the triphenylmethyl protecting groups may be removed by treatment of the tritritylpenta-O-methyl adduct of sucrose with acetic acid. Here the yields are low, possibly due to cleavage of sucrose to produce O-methylated glucose and fructose derivatives.
Any alkali metal can be used in the present procedure such as lithium, sodium and the like. Two alkali metals may also be used such as lithium and sodium. It is preferable, however, to use lithium in this reduction procedure, because it is relatively inexpensive, is less reactive than other group (I) metals in air, is safe to handle in air and is less pyrophoric than any other group (I) metals in the presence of moisture.
The tritylated penta-O-methylsucrose is diluted in tetrahydrofuran (THF) and liquid ammonia. It is preferable to use approximately 1 liter of tetrahydrofuran for every 100 grams of tri-O-trityl-penta-O-methylsucrose; however variations from this amount do not affect the yield of the final product. For example, 45 to 50 grams of tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose can be dissolved in 1.0 liter of tetrahydrofuran (THF), or 288 grams of tri-O-trityl-2,3,3',4,4'-penta-methylsucrose can be dissolved in 2.5 liters of THF. If 288 grams (253 mmol) of 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose is dissolved in 2.5 liters of dry tetrahydrofuran, then the mixture is cooled to -70� C. Into this solution is distilled approximately 2.5 liters of liquid ammonia, and the mixture is treated with small pieces of lithium (12 grams, 1,714 mmol, 6.7 equivalent). It is preferable to use 2 to 5 equivalent excess of lithium for each millimole of triphenylmethyl group present in the molecule. It is more preferable to use a minimum of 2 equivalent excess alkali metal per mole of the trityl moiety. The addition of the alkali metal generally takes place over a time period of 30 to 60 minutes depending upon the quantities involved. In this instance, the addition time is about 60 minutes. The color of the reaction mixture after addition of the alkali metal is deep red. The reaction mixture is allowed to stir for about three hours at a temperature between -65� C. to -78� C, more preferably at -70� C. The excess alkali metal is then decomposed by the addition of ethanol or isoproponal. However, it is preferable to use ethanol, since it can be easily removed in vacuo. Approximately 0.1 ml of ethanol is added per millimole of alkali metal used. Small pieces of solid carbon dioxide are also added after destroying the lithium metal to aid in the evaporation of ammonia as the solution is allowed to attain room temperature.
The resulting mixture is then filtered, the inorganic retentate is washed thoroughly with acetone, and the effluent is concentrated to a thick yellow oil. Flash column chromatography of the concentrated oil on a column of silica gel using 50% ethyl acetate in methylene chloride separates the triphenylmethane and other nonpolar components of the reaction mixture. 2,3,3',4,4'-Penta-O-methylsucrose is then eluted from the column with 10% ethanol in methylene chloride.
The yield of the 2,3,3',4,4'-penta-O-methylsucrose from this isolation procedure is 95% to 97%.
Approximately between 2.06 grams (5 mmol) to 14.27 grams (34.62 mmol) of 2,3,3',4,4'-penta-O-methylsucrose in about 60 to 200 ml of a suitable solvent such as acetonitrile, dimethyl acetamide, pyridine and mixtures thereof; more preferably 6.2 grams (15.04 mmol) of 2,3,3',4,4'-penta-O-methylsucrose in about 150 ml of pyridine is then added to any trisubstituted phosphorus compound such as triphenylphosphine, triethylphosphine and the like. It is preferable to use triphenylphosphine followed by addition of a carbon tetrahalide of choice. The amount of triphenylphosphine used may vary depending on the amount of 2,3,3',4,4'-penta-O-methylsucrose used. For instance, between 7.8 grams (30 mmol) to 32.65 grams (124.6 mmol) of triphenylphosphine, preferably 14.16 grams (54 mmol) can be used. It is most preferable to use 3.6 equivalents of triphenylphosphine.
After the addition of triphenylphosphine any tetrahalomethane may be used based upon the desired X substituent (where X=Cl, Br or I) in the compound of structure (I). For example, if one desires a dichloro-dideoxy hexa-O-methylsucrose product, then the tetrahalomethane used has chlorine moieties. Examples of the tetrahalomethanes that can be used in the present invention include carbon tetrachloride, carbon tetraiodide, carbon tetrabromide and the like.
The amount of the tetrahalomethane that is used may vary depending upon the amount of 2,3,3,,4,4'-penta-O-methylsucrose and triphenylphosphine used. The amount of tetrahalomethane may vary between 4.615 grams (30 mmol) to 19.193 grams (124.63 mmol). It is preferable to use 8.312 gram (54 mmol) of tetrahalomethane in the present invention. The addition of the tetrahalomethane usually takes place at ambient room temperature that may vary between 20� C. to 28� C. It is preferable to add the tetrahalomethane at a temperature of 25� C.
After addition of the tetrahalomethane, the contents are then further stirred vigorously and allowed to attain a temperature of about 60� C. over about 40 minutes. After the reaction has reached the temperature of 60� C., the reaction is monitored to ensure that all of the starting material is consumed by aliquoting a 10 μl sample from the reaction every 15 minutes and running a TLC plate in ethyl acetate (silica gel 60, E Merck). Generally, all of the starting material is consumed between 60 to 75 minutes.
Methanol, ethanol or propanol is then added to the reaction mixture to stop the reaction. It is preferable to use methanol since it can be conveniently removed in vacuo. The amount of methanol added to the reaction is not critical and may range from 50 to 300 ml. The amount used may vary depending on the amount of penta-O-sucrose used in the reaction. For instance, it is preferable to use about 100 ml for 6 grams of the penta-O-methylsucrose used in the reaction or 300 ml for 14 grams of the penta-O-methylsucrose. The contents are then cooled to room temperature and concentrated to a paste in vacuo.
The residue is then dissolved in ethyl acetate and washed three times with 10% aqueous hydrogen peroxide. The organic layer is separated and placed in a refrigerator for a few hours or overnight to allow the triphenylphosphine oxide to precipitate. The phosphine oxide is removed by filtration and the effluent adsorbed onto silica gel (100 grams) and further concentrated to a dry, free-flowing powder. The silica gel-coated mixture is then carefully poured onto a column of silica gel and eluted with 30% ethyl acetate in hexanes to provide a 6,6'-dihalo-6,6'-dideoxy-2,3,3',4,4'-penta-O-methylsucrose as an oil.
6,6'-Dihalo-6,6'-dideoxy-2,3,3',4,4'-penta-O-methylsucrose is then diluted in methylene chloride and treated with boron trifluoride etherate, followed by addition of excess diazomethane in methylene chloride to methylate the 1'oxygen moiety.
A solution of the dihalide, generally between 646 milligrams (1.44 mmol) to 28.55 grams (63.56 mmol) is used, more preferably 4.28 grams (9.53 mmol). The dihalide solution is cooled to a temperature of about -10� C. Between 10 μl to 100 μl of boron trifluoride etherate is added to this solution. It is preferable to add between 50 μl to 70 μl of boron trifluoride etherate. The boron trifluoride etherate is added dropwise to the cooled dihalopenta-O-methylsucrose in methylene chloride solution.
After the boron trifluoride etherate is added an excess amount of diazomethane in methylene chloride is added very slowly as a stream to the solution at -10� C. Subsequently, it is critical to add the boron trifluoride etherate very slowly to the solution and the solution must be cooled to -10� C. to prevent an explosion. This reaction is spontaneous and thus the solution is then filtered immediately after the addition of the boron trifluoride etherate and is washed serially with sodium bicarbonate, water and brine. The organic layer is then separated and dried over anhydrous magnesium sulfate prior to concentrating this layer in vacuo. 6,6'-Dihalo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose is the product which is obtained as an oil. Alternatively, the solution following the treatment with diazomethane can be briefly purged with argon, poured over a short bed of silica gel in a sintered glass funnel, filtered, and the effluent collected. The silica gel bed is washed with ethyl acetate in hexanes (1:1) to recover all the product. The organic layers are concentrated in vacuo to provide the dihalo-dideoxy-hexa-O-methyl adduct as an oil.
6,6'-Dihalo-6,6'-dideoxy-1',2,3,3',4,4'-hexa-O-methylsucrose may be used as an intermediate in the synthesis of polyethers. Synthesis of polyethers from the dihalide may be accomplished by using reactions such as the known Williamson ether synthesis. In this synthesis nucleophiles are generated from bishydroxide compounds such as bisphenolmethanes, ethylene glycol, dihydroxypropane and the like upon treatment with non-nucleophilic bases such as sodium hydride, lithium hydride, potassium hydride and the like to form bis alkoxides. The bisalkoxides are then treated with the dihalide compounds of the present invention, which act as electrophiles to generate polyethers of alkyl and aryl diols and the 6,6' dihalides described above.
Another alternative to the Williamson synthesis would be a phase-transfer method wherein the dihalide is reacted with 1,4 dihydroxymethylenecyclohexane diols in the presence of a base, as described above, and a suitable solvent to produce polyethers.
The novel alkyl or aryl polymers can also be produced by methods known in the art such as by nucleophilic displacement of the halide or by electrophilic activation of the halide followed by nucleophilic displacement with allyl or aryl bisnucleophiles. These and other methods are well known in the art.
Moreover, the compounds of the present invention can also be used as intermediates in the synthesis of chiral resolving agents, chiral auxiliaries, for asymmetric synthesis, chiral organometal and coordination complexes. Because naturally occurring materials such as sucrose and derivatives thereof are asymmetric, they can be used in conjunction with other organic or inorganic materials to produce coordination or organometallic complexes which show proclivity to attack one face or the other of a double bond with high selectivity. This selective mode of attack is known as asymmetric synthesis and the agent effecting the transformation is called an asymmetric reagent. Thus, the presently disclosed dihalo-dideoxy-hexa-O-methylsucrose compound can be further used to synthesize asymmetric reagents that can be used in conjunction with certain metals to facilitate the synthesis of rare medicinal agents, sugars and the like. Because the 6 and 6' ends containing the chlorine substituents are stearically nonequivalent, this dihalide can be transformed to unusual hydroxy acids, or amino acids. The dimerization of these compounds may lead to new ionophores.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.
The procedure of Hough, Mufti, and Khan, Carbohydrate Res., Vol. 21, pp. 144-147 (1972), is modified as shown below. To a solution of 15 g of sucrose (43.82 mmol) in 225 ml of pyridine, a solution of 54.95 g of trityl chloride (197.1 mmol, 4.5 equiv.) in 50 ml of pyridine is added dropwise over a period of 30 minutes. The reaction mixture is then stirred at room temperature for 4 days. After 4 days, the solution is concentrated to a brown syrup, which is dissolved in methylene chloride. This solution is further washed successively with 1M hydrochloric acid, saturated sodium bicarbonate solution, water, and brine and then dried over anhydrous sodium sulfate. The methylene chloride solution is then concentrated in vacuo and the residue applied on a column of silica gel packed in methylene chloride:acetone (4:1) and eluted with that solvent. The 1',6,6'-tri-O-tritylsucrose is obtained (28.59 g) in 58.8% yield as an off-white solid with a melting point of 127� to 130� C.
On scales larger than 40 mmol, the following procedure can be used. However, the yields established in the method shown are reproducible on scales ranging from 1 mmol to 210 mmol.
In a dry 5-L four-neck flask is dissolved 70 grams of sucrose (204.5 mmol) in 1 liter dry dimethylformamide (DMF) and dry triethylamine (200 ml, 145 grams, 1,423 mmol). The solution is allowed to attain a temperature of 25� to 30� C. and treated with a solution of trityl chloride (260 grams, 935.2 mmol, 4.5 equiv.) in dimethylformamide (600 ml), added dropwise over 1 hour. After the addition is complete, the reaction mixture is heated to a temperature of 50� C. and allowed to stir for 48 hours at that temperature. After 2 days, the reaction mixture is filtered through a short pad of silica gel to remove the precipitated triethylammonium hydrochloride and the residue is washed with methylene chloride:acetone (4:1). The effluent is then concentrated to a residue, which is reconstituted in methylene chloride and washed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution, water, and brine and then dried over anhydrous sodium sulfate. The dry organic extract is then filtered and concentrated in vacuo to provide a yellow foamy solid. This material is then applied on a silica gel column (230 to 400 mesh, 10 cm�50 cm) packed with methylene chloride and successively eluted with methylene chloride, then 10% acetone in methylene chloride, followed by elution with 20% acetone in methylene chloride. The desired tri-O-tritylsucrose elutes with 20% acetone in methylene chloride and has an Rf of 0.21 in the same solvent. The amount of 1',6,6'-tri-O-tritylsucrose obtained by this method of synthesis and isolation is typically between 146 to 150 grams or 67% to 68.8%. On scales between 1 mmol and 50 mmol(314 mg to 15.7 grams) yields average about 76%.
FIGS. 2 and 3 illustrate the respective NMR spectra of 1',6,6'-tri-O-tritylsucrose.
On scales larger than 10 mmol the following procedure is used. To a dry 5 liter four-neck flask is added sodium hydride (60% in oil, 150 grams, 1250 mmol), washed free of oil with pentane and suspended in DMSO (800 ml). The suspension is heated to 50� C., mechanically stirred, and treated with a solution of 1,6,6'-tri-O-tritylsucrose (50 grams, 46.76 mmol, dissolved in DMSO 200 ml, and added dropwise over 2 hours). The temperature of the reaction is monitored internally and maintained between 50� C. and 55� C. during the course of addition and 90 minutes thereafter. After hydrogen evolution has ceased completely, the burgundy-red solution is cooled to 25� C. and treated with dimethyl sulfate (147.5 grams, 1175 mmol, 111 ml, added dropwise over 90 minutes). The reaction is stirred at room temperature for 24 hours, treated with aqueous sodium hydroxide (10% solution, 500 ml), and stirred for an additional 3 hours. The mixture is then diluted with water (500 ml) and methylene chloride (500 ml) and the phases separated. The aqueous layer is re-extracted with methylene chloride (4�300 ml), then the organic extracts are combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The glassy residue is flash-chromatographed over a column of silica gel (10 cm�15 cm) and eluted with hexanes:methylene chloride (1:1, 2 L), then methylene chloride (2 L) followed by 5% ethyl acetate in methylene chloride (2 L), at a flow rate of about 200 ml/min. The isolated product (mp 103�-108� C.) weighed 47.1 grams (41.35 mmol) and a 89% yield is obtained. Rf of the tritylated methylsucrose is 0.15 in methylene chloride and [α]D 27 =47.68� in methylene chloride. FIGS. 4 and 5 illustrate the respective NMR spectra for this product. The NMR data provided: 1 H NMR (500.11 MHz, acetone-D6) δ 3.04 (H-2, dd, J=3.5, 9.5 Hz), 3.06 (H-1'a, d, J=10 Hz), 3.07 (H-6a, dd, J=3, 10 Hz), 3.14 (OMe-3', s), 3.16 (OMe- 4', s), 3.19 (OMe-2, s), 3.21 (H-3, t, J=9.5 Hz), 3.31 (OMe-4, s), 3.36 (H-1'b, d, J=10 Hz), 3.41 (OMe-3, s), 3.41 (H-6b, J=2, 10 Hz), 3.51 (H-6'a, m), 3.53 (H-4, dd, J=9.5, 10 Hz), 3.55 (H-6'b, m), 3.88 (H-5, ddd, J=2, 3, 10 Hz), 4.17 (H-3, d, J=8.5 Hz), 4.29 (H-4', t, J=8.5 H), 4.41 (H-5', m), 5.98 (H-1, d, J=3.5 Hz), 7.34 (30H arom), 7.52 (15H arom). 13 C NMR (125.76 MHz, acetone-D6) δ 57.73 (OMe-3'), 58.36 (OMe-4'), 58.68 (OMe-2), 60.46 (OMe-4), 60.60 (OMe-3), 62.97 (CH2 -6'), 63.89 (CH2 -6), 67.86 (CH2 -1'), 71.41 (CH-5), 79.52 (CH-5'), 80.17 (CH-4), 81.50 (CH-4'), 82.35 (CH-2), 84.52 (CH-3), 86.74 (1'-C-trityl methine), 86.93 (CH-3'), 87.51 (6-C-trityl methine), 87.68 (6'-C-trityl methine), 88.92 (CH-1), 104.66 (CH-2'), 127.22 (CH), 127.43 (2CH), 128.07 (2CH), 128.23 (3CH), 128.27 (CH), 129.03 (2CH), 129.14 (4CH), 144.05(C); 144.32 (2C); FAB mass for C74 H74 O11 calculated 1138.33; found M+ +1=1139, M+ -H+K+ =1177, M+ + K+ =1178. Anal. calc for C74 H74 O11 : C, 78.0; H, 6.5; O, 15.5. Found C, 77.5; H, 6.5.
After scale-up of this reaction employing 150 g tri-O-tritylsucrose (140 mmol), 150 g of sodium hydride (60% in oil, 3,900 mmol); 1,600 ml of dimethylsulfoxide; and 330 ml of dimethylsulfate (441 g, 3,500 mmol) was performed under exactly the same conditions discussed above. After chromatography on a column of silica gel (230 to 400 mesh, 10 cm�50 cm) and elution with three times the quantities of solvents discussed above, 145.15 g of tri-O-trityl-penta-O-methylsucrose was obtained in 91% yield.
To a 40 mmol solution of 1',6,6'-tri-O-trityl-2,3,3',4,4'-penta-O-methylsucrose (45.6 grams) in 1 liter of dry tetrahydrofuran and 2 liters of liquid ammonia at -70� C. are added 4 grams of small pieces of lithium wire. The lithium wire is added over a period of over 50 minutes and a deep-red solution is obtained. This solution is further stirred for 3 hours at -70� C. The excess lithium is decomposed by adding 60 ml of ethanol. Small pieces of solid carbon dioxide are also added to aid the evaporation of ammonia as the solution approaches room temperature. The resulting mixture is then filtered, and the inorganic retentate is washed thoroughly five times with 300 mls of acetone. The effluent is then concentrated to a thick yellow oil.
The product is then purified by flash column chromatography according to the guidelines of Still, Kahn and Mitra, J. Org. Chem., Vol. 43 (1978), pp. 2923-2925, on 230-400 mesh silica gel.
The oil is then placed on a silica gel column (10 cm�15 cm) and is washed with a solution containing 50% ethyl acetate in methylene chloride at a flow rate of 200 ml/min. This wash separates out the triphenylmethane and other nonpolar components of the reaction mixture.
2,3,3',4,4'-penta-O-methylsucrose is eluted from the column with a 10% ethanol in methylene chloride solution. 16.11 Grams, 39.10 mmol of 2,3,3',4,4'-penta-O-methylsucrose is obtained, and the yield of this product is 97%. Rf in 5% ethanol in methylene chloride is 0.31 and [α]D 27 =50.60� in acetone. 1 H NMR (500.11 MHz, acetone D6) δ 3.15 (H-4, t, J3,4 =5.1 Hz, J4,5 =9.0 Hz), 3.15 (H-2, dd, J1,2 =3.7 Hz, J2,3 =9.8 Hz), 3.33 (H-1'a, d, J1'a,1'b =-12.5 Hz), 3.38 (OMe-4', s), 3.40 (H-3, t, J3,4 =9.8 Hz), 3.46 (OMe-3', s), 3.50 (OMe-2, s), 3.53 (OMe-4, s), 3.55 (OMe-3, s), 3.55 (H-1' b,d), 3.59 (H-6'a, m, J6'a,6'b =12.0 Hz), 3.60 (H-6a, dd, J5,6a =5 Hz, J6a,6b =-10.6 Hz), 3.61 (H-6'b, m J6'a,6'b =-12.0 Hz), 3.75 (H-6b, dd, J5,6b =2.1 Hz, J6a,6b =-10.6 Hz), 3.78 (H-5, m, J5,6a =5 Hz, J5,6b =2.1 Hz), 3.80 (H-4', t, J3',4' =5.1 Hz, J4',5' =5.8 Hz), 3.84 (H-5', m, J5',6'a =4.2 Hz, J5',6'b =6.3 Hz), 3.87 (H-3', d, J3',4' =5.1 Hz), 5.45 (H-1, d, J1,2 =3.7 Hz). 13 C NMR (125.76 MHz, acetone D6) δ 57.96 (OMe-4'), 58.98 (OMe-3'), 59.76 (OMe-2), 60.29 (CH2 -6), 60.39 (OMe-4), 60.67 (OMe-3), 61.79 (CH2 -6'), 64.63 (CH2 -1'), 73.12 (CH-5), 79.53 (CH-2), 82.48 (CH-4), 82.59 (CH-5'), 84.24 (CH-3), 84.52 (CH-4,), 87.48 (CH-3'), 90.17 (CH-1), 106.80 (C-2'). FDMS for C17 H32 O11 calculated 412.43; found M+1=413. FIGS. 6 and 7 illustrate the respective NMR spectra of 2,3,3',4,4'-penta-O-methylsucrose. Anal. calc for C17 H34 O11 : C, 49.5; H, 7.5; 0, 42.8. Found: C, 49.2; H, 7.8.
To a solution containing 2,3,3',4,4'-penta-O-methylsucrose (6.2 g. 15.04 mmol) in pyridine (150 ml) is added triphenylphosphine (14.16 g, 54 mmol, 3.6 equiv.) followed by carbon tetrachloride (8.31 g, 5.19 ml, 54 mmol) at 25�. The contents are stirred vigorously and allowed to attain a temperature of 60� over 40 min., then maintained at that temperature for an additional 30 min. To this mixture is added methanol (100 ml), then the contents are cooled to room temperature and concentrated to a paste in vacuo. The residue is redissolved in ethyl acetate and washed with 10% hydrogen peroxide (3�100 ml). The organic layer is then adsorbed onto silica gel (100 g) and further concentrated to a dry, free-flowing powder. The silica gel-coated mixture is carefully poured onto a column (5 cm�15 cm) and eluted with 30% ethyl acetate in hexanes to provide 6,6'-dichloro-6,6'-dideoxy-2,3,3',4,4'-penta-O-methylsucrose as an oil (6.2 g, 13.8 mmol, 91.7% yield). Rf of 6,6'-dichloro-6,6'-dideoxy-2,3,3',4,4'-penta-O-methylsucrose in 50% ethyl acetate in hexanes is 0.29, [α]D 26 =40.13 in acetone. This compound is used immediately without further characterization.
A solution of dichloro-dideoxy-penta-O-methylsucrose (6.2 g, 13.8 mmol) in methylene chloride (50 ml) at -10� C. is treated with boron trifluoride etherate (70 μl), followed by addition of excess diazomethane in methylene chloride (approximately 0.7M, 100 ml, 70 mmol). After about 5 min, the cold solution is filtered and washed serially with saturated sodium bicarbonate, water, and brine. The organic layer is dried over anhydrous magnesium sulfate and concentrated in vacuo to provide the dichlorohexa-O-methyl ether as an oil (6.33 g, 13.66 mmol, 99% yield). This compound needed no further purification. Rf of 6,6'-dichloro-6,6'-dideoxy, 1,2,3,3',4,4'-hexa-O-methylsucrose in 50% ethyl acetate in hexanes is 0.48, [α]D 25 =58.15�. 1 H NMR (500.11 MHz, acetone-D6) δ 3.07 (H-4, dd, J=9, 9.5 Hz), 3.08 (H-2, dd, J=3.5, 9.5 Hz), 3.36 (H- 1'b, d, J=11 Hz), 3.38 (H-3, t, J=9.5 Hz), 3.38 (OMe-1', s), 3.43 (OMe-2, s), 3.46 (OMe-4', s), 3.47 (OMe-3', s), 3.53 (OMe-4, s), 3.53 (OMe-3, s), 3.58 (H-1'a, d, J=11 Hz), 3.75-3.92 (6H, m), 4.01 (H-3', d, J=7 Hz), 4.01 (H-5, ddd, J=2.5, 5, 9.5 Hz), 5.51 (H-1, d, J=3.5 Hz). 13 C NMR (125.76 MHz, acetone D6) δ 45.60 (CH2 -6), 46.25 (CH2 -6'), 58.20 (OMe-2), 58.31 (OMe-4'), 58.49 (OMe-3'), 59.08 (OMe-1'), 60.33 (OMe-3), 60.35 (OMe-4), 71.03 (CH- 5), 73.99 (CH2 -1'), 80.56 (CH-4), 81.10 (CH-5), 82.21 (CH-2), 83.75 (CH-3), 85.75 (CH-4'), 85.98 (CH-3'), 89.96 (CH-1), 105.2 (C-2'). Anal. Calc. for C18 H32 O9 Cl2 : C, 45.6; H, 6.9; O, 31.1; Cl, 15.5. Found: C, 45.7; H, 6.9; Cl, 15.2. FIGS. 8 and 9 are NMR spectra of this final product.
While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.
|Cited Patent
|Filing date
|Publication date
|Dec 30, 1957
|Mar 8, 1960
|Dow Chemical Co
|Ether-esters of sucrose
|Apr 11, 1960
|Feb 23, 1965
|Monsanto Co
|Sucrose ethers
|Dec 11, 1975
|Sep 26, 1978
|Tate & Lyle Limited
|Preparation of sucrose 6,6'-dichloro hexa-acetate
|Sep 12, 1983
|Sep 16, 1986
|Tate & Lyle Public Limited Co.
|Trichloro, 6-substituted sucrose compounds, compositions and uses therefor
|Oct 31, 1984
|Apr 7, 1987
|Georgetown University
|Galactose-C-6 nitrogen mustard compounds and their uses
|Feb 24, 1987
|Jul 25, 1989
|Biocarb Ab
|Method for diagnosing the presence of bacteria
|May 3, 1989
|Dec 25, 1990
|Tate & Lyle P.L.C.
|Brominated sucrose derivatives, compositions and methods of use
|"Synthesis of Partially Methylated Sucrose Derivatives" O'Donnell et al.; Aust. J. Chem. 25-407-412 (1972).
|Dirlikov, "Monomes and Polymers based on Mono-and Disaccharides," Pacific Polymer Preprints, vol. 1, (Dec. 12-15, 1989), pp. 113-114.
|Dirlikov, Monomes and Polymers based on Mono and Disaccharides, Pacific Polymer Preprints, vol. 1, (Dec. 12 15, 1989), pp. 113 114.
|Hough et al., "Sucrochemistry. Part II, 6,6'-Di-O-Tritylsucrose", Carbohyd. Res., vol. 21 (1972), pp. 144-147.
|Hough et al., Sucrochemistry. Part II, 6,6 Di O Tritylsucrose , Carbohyd. Res., vol. 21 (1972), pp. 144 147.
|Ogata et al., "Molecular Weight Control in Polycondensation of Hydroxyl Diesters with Hexamethylenediamine by Polymer Matrices", Journal of Polymer Science: Polymer Chemistry Edition, vol. 19 (1981), pp. 2609-2617.
|Ogata et al., Molecular Weight Control in Polycondensation of Hydroxyl Diesters with Hexamethylenediamine by Polymer Matrices , Journal of Polymer Science: Polymer Chemistry Edition, vol. 19 (1981), pp. 2609 2617.
|Synthesis of Partially Methylated Sucrose Derivatives O Donnell et al.; Aust. J. Chem. 25 407 412 (1972).
|Whistler et al., "Preferential Halogenation of the Primary Hydroxyl Group",Methods in Carbohydrate Chemistry, vol. VIII (1980), pp. 227-231.
|Whistler et al., Preferential Halogenation of the Primary Hydroxyl Group , Methods in Carbohydrate Chemistry, vol. VIII (1980), pp. 227 231.
|Citing Patent
|Filing date
|Publication date
|Jun 30, 1992
|Apr 25, 1995
|Hawaiian Sugar Planters' Association
|1',6,6'-triamino- and 6,6'-diamino- sucrose derivatives
|Jan 24, 1995
|Sep 12, 1995
|Hawaiian Sugar Planters' Association
|Platinum complexes of sucrose derivatives
|Jun 29, 1993
|Jan 6, 1994
|Hawaiian Sugar Planters' Association
|Novel sucrose ligands, methods for their preparation, platinum complexes derived therefrom, and methods for their usage
|U.S. Classification
|536/18.4, 536/18.5, 536/18.6, 536/120
|International Classification
|Cooperative Classification
|European Classification
|Dec 7, 1990
Owner name: HAWAIIAN SUGAR PLANTERS ASSOCIATION, HAWAII
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SACHINVALA, NAVZER D.;REEL/FRAME:005533/0588
Effective date: 19901207
|Dec 18, 1995
|Fee payment
Year of fee payment: 4
|Aug 20, 1996
Owner name: HAWAII AGRICULTURE RESEARCH CENTER, HAWAII
Free format text: CHANGE OF NAME;ASSIGNOR:HAWAIIAN SUGAR PLANTERS ASSOCIATION;REEL/FRAME:008094/0222
Effective date: 19960319
|Jan 25, 2000
|Maintenance fee reminder mailed
|Jul 2, 2000
|Lapse for failure to pay maintenance fees
|Sep 5, 2000
|Expired due to failure to pay maintenance fee
Effective date: 20000630


text:
Heavy Duty Mig
Air Compressors
Air compressors are useful mechanical devices that are used for the purpose of transforming power such as gas or electricity into another form of energy referred to as kinetic through a process called compression. Compression results from either filling and releasing air or accelerating and decelerating air. When air is compressed through either of these ways, it is has many uses. Air compressors are commonly used in a number of home improvement tools such as staplers and spray guns. They are also commonly used in the removal of rubbish and they can be bought through a number of online resources.
Heavy duty air compressors are designed for industrial processes and offer more value for money because the air storage is long lasting and uses less energy for optimal functions. A quality air compressor should constitute essential safety features such as valves that allow the release of air in instances when the pressure in the tank is too much. Belt guards are other features that enhance the safety of the device.
Air tools require gas as a source of energy to perform their functions. This gas is typically derived from gas compressors that contain compressed air. Portable cylinders contain carbon dioxide that makes the device lighter and easier to move around with. A key advantage of air tools is that they are affordable in comparison to electric tools and they are easier to maintain. Air tools are also considerably much safer to use than those that are powered by electricity. Te portability and compact size do not comprise the ability of the tool to carry out essential tasks effectively. Many people use air tools around their homes and they can also be found in fully fledged industries. A light and portable air tool can effortlessly enable the user to perform tough jobs while providing impressive speed as well as heightened performance. Examples of air tools are drills, polishers and hammers.
MIG welders can be used for both domestic and commercial purposes. Air tools are especially useful when access to other forms of power is limited. It is important to choose the correct MIG welder based on what it is required. Welders are used for functions such as fabrication, repair and manufacturing. For MIG welding to be achieved, a wire feed is required. This wire is passed through a tip that is heated and the action of pulling the trigger causes the wire to melt thereby forming what is referred to as weld puddles. It is easy to learn how to go through the MIG welding process MIG welders are high in productivity and are not messy to use. They are also able to cater for various positions and metals like steel.
Sealey tools consist of quality products such as drill press vices, wrenches, saws, ventilators and screwdrivers. These tools are essential for any workshop or industry tasks. Pressure washers function by using a high amount of pressure that releases water for extensive cleaning purposes that involve cars, buildings and roads. Tool boxes help to ensure that everything is kept in order and that all the tools that one needs can be easily located. Good tool boxes should be portable with adequate compartments for storage.
About the Author
Clayton Shetley is the author of this article on Air Compressors. Find more information about Air Tools here.
Welding Gloves, Grain, L, Wing, BlueBlack, PR
' Extra Heavy Duty Welding Gloves, Application MIG/Stick, Leather Palm Type Grain, Palm Material Pigskin, Grade of Leather Premium, Back Material Cowhide/Silicone, Length 13 In., Lining Material Fleece/Foam/Aluminized, Stitching Material Kevlar(R), Color Blue/Black, Size L, Cuff 5 In. Gauntlet, Cuff Material Cowhide, Cut Split, Design 3-D, Thumb Style Wing, Use Extra Heavy Duty MIG/Stick Welding, …
Heavy Duty Thick Welding Gloves – Small Size Hands with Long Sleeves – For Stick TIG and MIG Welding – Premium Leather with Kevlar Lining – Dog and Cat Hand Scratch Animal Protection
Performing a wold class weld is something few people experienced but is something every passionate asspire to. You can't become one over night and great gear really do matter. We at Welder's Trust put extra care in providing welding professionals with the right gloves for the job. here's what you can expect from this Welder's Trust gloves: – Great heat insolation from thick cow leather – Soft lea…
Everlast Poweri-MIG 250 MIG Stick Welder, 220/240-volt, Green
The all new CC/CV Power i-MIG 250, is a versatile unit with the power to handle heavy welding chores around any home, shop, farm or commercial fabrication facility. This unit features it's own undercarriage with a place to carry a gas cylinder so it's completely self-contained and can roll around to reach anywhere you need it within the shop. Even though it's considered a roll-around unit, weight …
MIG 130 Welder Flux Core Wire Automatic Feed Electric Welding Machine
Product Description: – This is our brand new and high quality MIG-130 welder, which is particularly suitable for mild steel and stainless steel. – This welding machine integrates comfortable hand grip, easy operation and high precision. – It is variable Feed Speed Controlled and has optional 10 welding speed, which entirely promotes the work efficiency of its user. – In this kit, there are almost …
Daixers Portable Stainless Steel 9-in-1 Multifunction Outdoor Folding Plier,4-1/3Inch
- Include: Needle Nose Pliers , Folding Blade , Screwdriver , Pocket Screwdriver , Bottle Opener Keychain – Pocket Tool Set – Comfortable handles and spring-loaded functionality to reduce hand fatigue – Compact folding design- easy to use & Storage – Great for Outdoor,camping, or fishing and ect…
Everlast Boxing Kit 70lb Heavy Bag, Gloves, Hand Wraps and Leather Swivel Mount Speed Bag, 4-Piece
The Everlast 70 Lbs Heavy Bag Kit is your key to fitness. Designed to help you work out and develop better swinging skills, it's both functional and durable. To start training and conditioning in style, you need a lightweight punching bag like the one included with this boxing bag kit. With this set, you can kick into action in no time while working out your muscles and staying fit. Try shadow bo…
Luxlady Premium Apple iPhone 6 iPhone 6S Flip Pu Leather Wallet Case IMAGE ID: 25006183 Zebra Longwing
Designed for Regular Size iPhone 6/6s (4.7″ display), NOT for iPhone 6/6s Plus (5.5″ display)! Features: – Designed exclusively for regular size iPhone 6 & iPhone 6s; – Premium PU leather, presents good-looking and durability; – Magnets with strong absorption but quite easy to detach, guarantees security & convenience; – Precise cutouts for all ports, camera, mic, speaker, and stylus; -Build in Ca…


text:
F**k Censorship! | Baltan Laboratories
Memes as an encryption language for political activism in the digital realm
A workshop to develop practical strategies to use memes as a medium to escape censorship methods such as image recognition control, word targeting and data crossing.
Baltan Basement / Saturday 27 May, 13:00-18:30. Tickets: €22,50 (regular) - €15,50 (students). You can buy your ticket on the Eventbrite page of the workshop: https://goo.gl/K5SK5M
A workshop by Memedom of Expression, developed in collaboration with the Asociación de Arte Útil.
Lees artikel | Via Baltan
27 mei 2017


text:
Deprecated: Non-static method C_Photocrati_Settings_Manager::get() should not be called statically, assuming $this from incompatible context in /nas/content/live/scgh/wp-content/plugins/nextgen-gallery/products/photocrati_nextgen/modules/nextgen_gallery_display/class.displayed_gallery.php on line 132
Deprecated: Non-static method C_Photocrati_Settings_Manager_Base::get() should not be called statically, assuming $this from incompatible context in /nas/content/live/scgh/wp-content/plugins/nextgen-gallery/non_pope/class.photocrati_settings_manager.php on line 272
By Debra Atlas
NEW YORK — The Occupy Wall Street protest has rapidly become a global phenomenon that offers a window into a different type of ecological unit: a totally organic type of social organization.
Begun on September 17 with 2,000 people gathering in lower Manhattan and marching uptown to Broadway, this movement has since been repeated across America. At least 82 countries and thousands of protesters have been involved in similar movements, such as Spain, in recent months.
Occupy Wall Street participants span a diverse range of backgrounds, age groups and beliefs. Crowds consist of students, families, the elderly, construction workers who join in on their lunchtime, business people, unemployed Wall Street executives, Iraq and Afghanistan veterans, parents, and others.
The ongoing protest is a movement created and nurtured by the Internet. Tweets and Facebook messages are constantly providing updates to those around the world.
But perhaps there is more to this growing sit-in than just protesters speaking out against bank bailouts, corporate greed, and the unrestrained power of Wall Street in Washington, DC. The rallying cry: "We are the 99 percent!" may be the catalyst for change, an opportunity for participants literally create something that is unique.
Americans are rallying to this cause. People from across the country are sending clothing, supplies, money, even notes of support. As varying needs arise among those gathered, new services are quietly made available to fill them.
The group BMW Guggenheim Lab—a mobile laboratory that has traveled to nine urban cities around the world over the course of six years—met with the organizers of New York's Occupy Wall Street and members of the community to discuss and examine issues that are affecting our cities. Their purpose is to generate "solutions from the people."
These continuing protests are changing conversations—on the street and in the national media. A recent news program on CNN featured three journalists examining the issues behind the protest at New York's Zuccotti Park, renamed Liberty Square by the crowds.
Two of the news aficionados were baffled as to why Mayor Bloomberg did not bring in the riot police and clear the crowds, as they were squatting on private property which the owners wanted to clear and clean up. The third journalist tried unsuccessfully to get the message across to the others of the purpose and importance of what the protesters were trying to do. He grasped the point that they were standing up for what they felt was right, that this was a movement that had captured the imagination and emotions of the general public and that the mayor was being wise to allow them to stay. His message clearly fell on deaf ears.
The idea that so many people from so many different walks of life are engaging in this ever-expanding protest, this "people's assembly"—ranging in the thousands in New York City alone—could well be birthing something with creativity and freedom that will last for years to come.
Check out more articles by Debra Atlas.


text:
Iraq Slams Kurds as Troop Dispute Restarts
Less Than a Week After 'Deal' the Same Argument Begins Anew
With both sides at the time talking up tensions leading to a civil war, Iraq's central government and the Kurdistan Regional Government (KRG) reached a deal to redeploy out of the disputed area between their borders.
That was last week, and the two are at it again, with the troops once again being sent back into the area and both sides blaming the other for another standoff.
KRG Prime Minister Nechirvan Barzani accused Maliki of being paranoid about conspiracies against him, while adding that he believes recent Iraqi military efforts to acquire more advanced weapons are primarily about attacking Iraqi Kurdistan, not defending territory.
Though the specific troop dispute is somewhat recent, the dispute between Iraq and Kurdistan is long-standing, with the KRG having successfully carved out an impressive level of autonomy and now hoping to expand its reach to other ethnically Kurdish areas along that border, particularly in the oil-rich area around Kirkuk. With oil distribution deals a big source of tension between the two sides, this is going to be a protracted battle.
Last 5 posts by Jason Ditz
- South Sudan President Announces Unilateral Ceasefire - May 22nd, 2017
- US Arms Makers' Stocks at Record Highs on Saudi Deal - May 22nd, 2017
- NATO Presents Montenegro's Membership as Big Victory Over Russia - May 22nd, 2017
- House Seeks Details on Increasing Permanent US Military Presence in Europe - May 22nd, 2017
- Palestinian Rights Not a Topic of Discussion During Trump's Visit - May 22nd, 2017


text:
How to start a car valeting business
If you're passionate about cars, have strong attention to detail and excellent customer service skills, a car valet business could be for you…
Useful links
What is a car valeting business and who is it suited to?
Creating a car valeting business plan
Car valeting rules and regulations
How much does it cost to start a car valeting business?
How much can you earn running a car valeting business?
Tips and useful contacts
How much can you earn running a car valeting business?
There are many variables that could impact the profitability of your car valeting business, ranging from local demand to the type of vehicles you choose to work with and your approach to marketing your business.
CK Detailing's Keir says that the money you make depends largely "on your location" and "the level of care you carry out", but suggests that a standard valet "can expect to earn about £25 to £35 for" for around one to two hours work.
If you plan to enter the luxury car detailing market – which CK Detailing operates in – and carry out premium car details "you can earn from a few hundred to the thousand pound mark per detail".
Keir adds that the best way to earn more from car valeting is simply to do a good job: "The car care industry relies heavily on word of mouth. If you're the best and people know about you, they will be willing to pay that bit more".
You should always be motivated to carry out work to the best of your abilities and to the best industry standards. This also goes for any employees you take on: provide ongoing training to teach them best practice and ensure your car valeting business is associated with a quality service.
Action point:
See if you can get a Start Up Loan to help you start a business idea
(external site, opens in new tab)
Keir also warns that you need to think carefully about your price point to ensure you attract customers: "When I initially set up my car care company I tried to undercut the competition, this backfired for me. People don't mind paying more for a better service. Don't overcharge though; people aren't going to use your business until you have a good reputation".
"Profits depend on the type of car valeting business", explains iValet UK's Tyler, "but an individual service provider can expect to profit around £8,000 trading first year from start-up or around £25,000 first year with a franchise".
Managing growth can be challenging for a new start-up and ensuring you maintain a steady cash flow is vital to keep your car valet business running smoothly. Think about how to sensibly reinvest your profits to grow organically as you build your reputation locally and beyond.
Tyler continues: "The easiest mistake is to wait for the phone to ring, just because you have a website and some social media adverts. Be active – knock on neighbours doors and build a reputation".
Even in an increasingly digital world, it's important not forget the importance of old fashioned marketing methods such as drop-door marketing, when growing your company, especially when you work in a customer-facing role that relies largely on local trade.
"Being a recognisable face for your business gives it a human side and can give you the edge over local competition.
Now you have all the knowledge you need to establish a successful car valeting company, take note of these useful tips and contacts for the car valeting industry…


text:
English translation of 'दवा की गोली'
दवा की गोली /dava ki goli/
nf/dava ki goli, davA kI golI, davaa kee golee, davā kī golī/
2. tablet countable noun
1. pill countable noun
Pills are small solid round masses of medicine or vitamins that you swallow.
2. tablet countable noun
A tablet is a small, solid, round mass of medicine which you swallow.
I take herbal sleeping tablets.
Copyright © 2014 by HarperCollins Publishers. All rights reserved.
Translation of दवा की गोली from the Collins Hindi to English Dictionary
Log in to comment on this word.


text:
Southeast Asia's biggest startup Sea said to file for $1b IPO
India: Flipkart signs term sheet to acquire beleaguered rival Snapdeal- Report
Exclusive: Kerry Group acquires China's Tianning Flavour & Fragrance
Exclusive: Global Founders Capital to invest up to $10m in Indonesia by year end
India: Kedaara Capital hits road to raise 2nd fund, IFC to invest up to $40m
South Korea's Taekwang to bid for Vietnam-based logistics firm Gemadept
Asia PE-VC Summit 2017 — Register now for 2x Insights & Networking
Malaysia's Lotte Chemical sets ceiling price for $1.4b IPO
Singapore: Gashub Group to list on ASX via RTO deal of Raffles Capital
SoftBank invests $100m in Brazilian ride-hailing app 99
Malaysia: Unlockd forms strategic partnership with Axiata in $23m Series B
Why Snapdeal debacle may compel Nexus to rethink its future course
India: Everstone raises investment in Servion Global to $74m
Lodha Group raises $375m from Cain Hoy for London residential project
Southeast Asia's biggest startup Sea said to file for $1b IPO
SG Dealbook: ST Engineering launches new JV, Ezion teams up with PIO
Singapore: Noble Group endures wild ride as talks continue with potential partners
Exclusive: Global Founders Capital to invest up to $10m in Indonesia by year end
PH blockchain platform Coins raises $5m series A extension led by Naspers
India: ASK Automotive to sell die-casting unit
Ebix to invest $120m for stake in digital payment provider ItzCash
Exclusive: Kerry Group acquires China's Tianning Flavour & Fragrance
India: Kedaara Capital hits road to raise 2nd fund, IFC to invest up to $40m
Australia's Champ Private Equity closes fourth fund at $547m
Australia: Blue Sky exits pharmacy services firm HPS for $114m
TP Therapeutics raises $45m co-led by China's Lilly Asia Ventures
China: CANBridge $25m Series B; VoxelCloud $10m Series A; Huajiao Live Video $14m funding
Vietnam: POPS completes series B round, in talks to raise series C
UrWork takes on WeWork in fight for shared spaces
India: UTI Asset Management to sell 26-30% stake through IPO this fiscal
Singapore: Gashub Group to list on ASX via RTO deal of Raffles Capital
Rocket-backed food takeaway Delivery Hero on course for listing
Malaysian telco giant Axiata buys 65% stake in Thai firm Suvitech
Sprint, SoftBank in informal merger talks with T-Mobile
Shanxi Meijin, China Broadband bid for $1.4b Singapore mobile carrier M1
Telecom operator Ooredoo prepares to launch mobile money services in Myanmar
India's $1.3t housing bonanza draws Piramal loan bet
Australia: QIC to acquire seven of Forest City's malls for $4b
China Life inks $950m recapitalization deal with US-based PE ElmTree Funds
India: Edutech startup Byju's aims to turn profitable this year
Sign up for our daily email on Asian M&As, PE, VCs, IPOs & Startups.
India: 10 promising tech startups tapping AI to disrupt industries
Lyft partners Waymo for self-driving car pilots
Tencent steps up AI push with research lab in Seattle
JPMorgan Chase & Co leaves blockchain consortium R3
Singapore: NTU to invest $5.7m in Big Data, AI lab
PE firm Gaja Capital begins talks to exit John Distilleries
Is Alipay entering Vietnam riding on Ascend Money deal?
Is CVC Capital looking to sell Chinese fast food chain Da Niang Dumplings?
© DealStreetAsia 2014 - 2016


text:
Written by Simon James
Illustrated by Simon James
Lovereading4kids Price £5.59
£6.99 saving £1.40 (20%)
Please login (or signup) to download the extract
You will need to Sign Up or Login before you can download a book extract.
To Sign Up all you need to do is give us your email address and a password and let us know the types of books you like. Thank you.
The Lovereading4Kids comment
Award winning Simon James is heart-warming in this story about the importance of dads! The terrifying tyrannosaurus rex is feared by all the creatures. He is very big, very fierce and has a very, very load ROAR. The only creature not afraid of him is the tiny dinosaur who hatches in his cave and adopts him as Dad. How a small creature and a very large creature bond and the roles they play in each others lives is wittily captured in text and pictures.
Rex by Simon James
This is a heart-warming story about being a dinosaur step-dad.
Once upon 400 million years ago a terrifying tyrannosaurus roamed the earth. He spent his days raging through the jungle scaring every dinosaur he saw with his fierce roar. One night, while he is sleeping, an abandoned egg cracks open and out pops a teeny, tiny baby dinosaur who immediately thinks that the tyrannosaurus is his dad! And so begins the touching story of a little dinosaur and his search for a dad.
This is a brilliant story for all dinosaur fans and also a sensitive look at relationships and growing up, perfect for families, schools and libraries.
About the Author
Other Formats
Book Info
40 pages
Interest Age: From 3
Simon James
More books by Simon James
Author's Website
Walker Books Ltd
Publication date
2nd April 2015
I love all the books they recommend & put up for me to review. I also love the fact that they give new authors the chance to share their booDaisy Pennock – age 15
I love Lovereading because I often never know what to read and this helps you find a good book. I have recommended this to many people.Shannon-Louise Masters – age 15
I love finding new books to read. My mummy and me look at the new ones coming out. I have written reviews of some of them!Jessica Cobbin – age 7
It is THE website to use for narrowing down your search for any book. Definitely knocks the socks off any other book review website.Nickey and Tomasz Hawryszczuk
It's a community united by a passion for books and promoting the best there is in children's literature.Sam Bateman and family
It's really exciting to read and review new books, thrilling to see my reviews online and I love finding the final published copies on sale.Sam Harper – age 10
Love "Lovereading4kids" as my son gets to hear about & read new books before his mates which keeps him interested in reading=a very happy MumLiz Evans
I love 'LoveReading 4 kids' because they let you read and learn things you'd never dreamed of learning before.Emily Horncastle – age 11


text:
Tom Cruise,
Mia Sara &
Tim Curry
Ridley Scott
Starring: Tom Cruise, Mia Sara & Tim Curry Director: Ridley Scott
There may never be another dawn.
13 copies available
|$9.25 Limited Time Only
|List Price:
|You Save:
|$5.73 (38% Off)
Available: Usually ships in 1-3 business days
Format: DVD
sku: ERDD
Brand New
Also released as:
Blu-ray Disc Features:
- Rated: Not Rated
- Run Time: 1 hours, 54 minutes
- Video: Color
- Released: May 31, 2011
- Originally Released: 1985
- Label: Universal Studios
- Encoding: Region 1 (USA & Canada)
- Note: Includes the director's cut with Jerry Goldsmith's score
- Feature commentary with director Ridley Scott
- Lost scenes
- Bryan Ferry music video
- Photo gallery
- Aspect Ratio: Widescreen - 2.35
- Audio:
- Dolby Digital 2.0 Stereo - English
- Dolby Digital 5.1 - English
- DTS Surround 5.1 - English
- Subtitles - French, Spanish
Performers, Cast and Crew:
|Tom Cruise, Mia Sara & Tim Curry
|Billy Barty, David Bennent, Cork Hubbert, Peter O'Farrell, Kiran Shah & Robert Picardo
|Directed by
|Ridley Scott
|Edited by
|Terry Rawlings
|Composition by
|Tangerine Dream
|Produced by
|Arnon Milchan
|Director of Photography:
|Alex Thomson
Entertainment Reviews:
Variety - 08/21/1985
"...Exhilarating visual elements....It is a fairy-tale produced on a grand scale, a classic tale of the struggle between darkness and light, good and evil..."
"...Exhilarating visual elements....It is a fairy-tale produced on a grand scale, a classic tale of the struggle between darkness and light, good and evil..."
Los Angeles Times - 04/18/1986
"...Awesome in its fantasy splendor....It is a sumptuous, richly colored feast for cinematographer Alex Gordon's camera..."
"...Awesome in its fantasy splendor....It is a sumptuous, richly colored feast for cinematographer Alex Gordon's camera..."
Uncut - 03/01/2012
3 stars out of 5 -- "It's beautiful to watch -- Scott's painterly settings are, as you'd expect, rich and detailed -- and Curry has fun as the bad guy."
3 stars out of 5 -- "It's beautiful to watch -- Scott's painterly settings are, as you'd expect, rich and detailed -- and Curry has fun as the bad guy."
Product Description:
Director Ridley Scott's lush fantasy film stars the young Tom Cruise as Jack, a peasant who lives in an enchanted forest with his beloved Lili (Mia Sara). One day, while quietly gamboling in a glade, the pair is distracted by the appearance of trolls, minions of the evil Lord of Darkness (Tim Curry). The cloven-footed, cavern-dwelling monster, long banished to the earth's nether regions, has sent the creatures on a mission to seize the horn of a unicorn, thereby plunging the planet into a frigid darkness over which he alone will reign. Things go from bad to worse as Lili succumbs to the forces of darkness, and Jack must assemble a motley band of elves to free her from bondage and return sunlight to the earth's surface. Sumptous art direction and overwhelming special effects are once again a testament to Scott's powers of visual invention.
Plot Synopsis:
In Ridley Scott's LEGEND, young Jack lives in a magic forest populated with friendly and exotic creatures. But the delicate balance between good and evil is upset when the Lord of Darkness seizes Jack's beloved, Lili, and a horn from one of the last unicorns, thereby gaining control of the universe. The plucky lad must then assemble a band of elves and do battle with the forces of evil to set Lili free and restore peace to the world.
Adventure | Fantasy | Medieval | Mythology | Witches And Wizards | Love Story | Good Vs. Evil | Epic | Recommended | Devil / Demons | Theatrical Release
Production Notes:
- Theatrical release: April 1986.
- Filmed on the James Bond set at Pinewood Studios in England. Production was delayed when the set burned down.
- The movie was screened on August 26, 1985, as the opening film of the Venice Film Festival.
- LEGEND marked Mia Sara's film debut.
- The European version of LEGEND is 20 minutes longer than the 89-minute American cut and features a Jerry Goldsmith score.
The Dark Crystal
$11.22 Super Savings
$10.83 Super Savings
$4.40 Super Savings
Eragon (Blu-ray)
$7.05 Super Savings
Labyrinth (Anniversary Ed.) (2-DVD)
$9.33 Super Savings
The Neverending Story
$5.21 Super Savings
Gamera: Legacy Collection, 1965-1999 (4-DVD)(4)
$7.98 on SALE
Alien Origin (Blu-ray)(20)
99¢ on SALE
When Dinosaurs Ruled the Earth (DVD-R)
$14.39 on SALE
The Arrival / Arrival 2 (DVD)(41)
$5.60 Super Savings
The Green Slime (DVD-R)(56)
$15.98 on SALE
TCM Greatest Classic Films Collection - Sci-Fi Adventures... (DVD)(33)
$9.98 on SALE
I Am Omega (DVD)(33)
$1.98 on SALE
Laserblast (DVD)(47)
$2.98 on SALE
Retro Underground Cinema - The Giant Spider (DVD)
$9.95 on SALE
Movie Lovers' Ratings & Reviews:
Customer Rating:
Based on 590 ratings.
Based on 590 ratings.
Be the first Movie Lover to write an online review of this product!
Similar Products
Sale Items:
Product Info
- Sales Rank: 22,978
- Shipping Weight: 0.15/lbs (approx)
- International Shipping: 1 item
Hopalong Cassidy - Ultimate Collector's Ed. (66-Film... (DVD)(31)
$29.98 on SALE
Dodge City (DVD)(73)
$5.98 on SALE
Sons of Kong: 10 Full-Length Movies on 3-DVDs (3D Pop-Up...(99)
$1.98 on SALE
NBC News - Deep Throat: Full Story of Watergate (DVD)(40)
99¢ on SALE
Charlie Chan: Castle in the Desert (DVD)
$11.98 on SALE
Get It On: The Seventies DVD Jukebox(6)
$2.98 on SALE
The In-Laws (1979) / The In-Laws (2003) (2-DVD)(28)
$4.98 on SALE
Dark Crimes: 50-Movie Collection (12-DVD)
$14.98 on SALE
The Computer Wore Tennis Shoes (DVD)(26)
$4.98 on SALE
To place an order or for customer service, call toll-free 1-800-336-4627 or outside the United States, call 1-610-649-7565
Open Monday-Friday: 8am-11pm, Weekends: 10am-10pm (Eastern Time)
Se habla Español! Spanish-speaking representatives available, Monday-Friday: 9am-4pm (Eastern Time)
Memorial Day: 10am-6pm
Memorial Day: 10am-6pm
Portions of this page © 2017 TiVo Corporation. For personal non-commercial use only. All rights reserved.
© 2017 OLDIES.com and its affiliates and partner companies. All rights reserved.
© 2017 OLDIES.com and its affiliates and partner companies. All rights reserved.


text:
Mitsubishi Eclipse Spyder
I have a bow top assembly new in
the package that I am looking to get
rid of. This part is discontinued and
is really hard to find or order
2 Answers
I would strongly suggest that you try to sell that on eBay, Craigslist, or on a Mitsubishi Eclipse enthusiasts on-line forum group. This is a Q&A Forum that doesn't engage in selling of car parts.
1 of 1 people found this helpful.
what he said
1 of 1 people found this helpful.
Your Answer
Search Mitsubishi Eclipse Spyder Questions
Mitsubishi Eclipse Spyder Experts
Reputation 1,710
Reputation 360
Daniel Foster
Reputation 260
Related Models For Sale
Used Mitsubishi Eclipse
29 Great Deals out of 1,359 listings starting at $1,000
Used Ford Mustang
472 Great Deals out of 45,735 listings starting at $1,999
Used Chevrolet Camaro
225 Great Deals out of 30,943 listings starting at $1,217
Used Mitsubishi Lancer Evolution
17 Great Deals out of 483 listings starting at $10,950
Used Chevrolet Corvette
120 Great Deals out of 20,753 listings starting at $3,000
Used Mazda MX-5 Miata
52 Great Deals out of 4,229 listings starting at $1,995
Used Mitsubishi 3000GT
84 listings starting at $2,999
Used Honda Civic
656 Great Deals out of 88,603 listings starting at $995
Used BMW 3 Series
974 Great Deals out of 31,729 listings starting at $1,000
Used Honda Civic Coupe
187 Great Deals out of 16,850 listings starting at $800
Used Cars For Sale
2012 Mitsubishi Eclipse Spyder For Sale
49 listings starting at $7,000
2011 Mitsubishi Eclipse Spyder For Sale
18 listings starting at $7,991
2010 Mitsubishi Eclipse Spyder For Sale
4 listings
2009 Mitsubishi Eclipse Spyder For Sale
46 listings starting at $4,995
2008 Mitsubishi Eclipse Spyder For Sale
59 listings starting at $4,500
Content submitted by Users is not endorsed by CarGurus, does not express the opinions of CarGurus, and should not be considered reviewed, screened, or approved by CarGurus. Please refer to CarGurus Terms of Use.


text:
The X Factor
The X Factor: Rachel Crow will stick to her gunsYoungster Rachel Crow has a song she wants to sing on The X Factor and she isn't going to let mentor Simon Cowell stand in her way.
The X Factor: Melanie Amaro, Josh Krajcik are the class of the fieldThe viewing public finally gets a say in what happens on The X Factor - it's been a long time coming, but it's finally here.
The X Factor: Simon and Paula together again?Here's the scoop according to tvguide.com Fox has ordered a second season of The X Factor, the network announced Wednesday.
The X Factor: Rating the finalists, at least in my opinionL.A. Reid and the Boys: Brian "Astro" Bradley - Brooklyn's hip-hop wonder kid. This 15-year-old has attitude to spare.
The X Factor: Top 12 decided, America finally gets to have a sayIt's been a long and, at times, bumpy road, but finally the viewers will have a say in who advances on The X Factor.
The X Factor: Rating the final 17 contestantsOn Tuesday night we found out who the final 17 acts would be on The X Factor. Here's what the judges and contestants had to say and some comments by ...
The X Factor: Top 16 revealed and I'm a little shocked SPOILER ALERTSPOILER ALERT SPOILER ALERT IF YOU LIVE ON THE WEST COAST STOP READING NOW. The X Factor's top 16, who will move on to the live shows, were ...
The X Factor: How did favourites do on home visits part twoHere's my thoughts on some of the performances from Part 2 of the judge's home visits on The X Factor: Chris Rene performed Everyday People for L.
The X Factor: It wasn't raining in CanadaWhat a great turn of events. I get home from work on Wednesday night prepared to delete the ALCS game between Texas and Detroit, which was delayed two hours by ...
The X Factor: Show postponed because of rainThat headline may sound a bit strange, but it's true. The X Factor was postponed on Wednesday due to rain - in Detroit.


text:
Explore Kindergarten Science, Teaching Science, and more!
Explore related topics
Watch as the blue and yellow water travel up the paper towel and makes it's way into the empty cup making green water. Neat!
How plants absorb water science experiment!
Walking Water experiment (and colour theory/ colour mixing too!)
12 Magic Reaction for the Best Baking Soda and Vinegar
Adventures of Adam DIY Toddler Water Wall
Gummy Bear Science ~ What a fun activity to start the year with! (Free.)
Expérience de sciences
Science in the kitchen
10 Science Experiments for Preschoolers ~ Creative Family Fun - tornado in a bottle, stages of matter, make a cloud, siphon water, how sound is made, diet coke & mentos, how water travels through a plant
Household science project. by caitlin