text:
The name of the organization shall be the Mohawk College Alumni Association (MCAA).
1. General Responsibilities
The Chair of the Mohawk College Alumni Association Council (MCAAC) upholds the MCAAC Mission, Vision and Values, Advisory Guidelines, Belief Statement, Terms of Reference and Charter.
The Chair of the MAAC is responsible for facilitating highly effective Council performance.
The Chair is not an executive of MCAAC in the sense that the Chair is not responsible for the operational management. In discharging his/her responsibility, the Chair:
- provides leadership to the Council on specific issues;
- is responsive to the ongoing needs of Council;
- in accordance with the direction of the Council, acts as the spokesperson for the Council;
- at the request of the Council and/or the Director, Alumni Relations, acts as an intermediary between the Council and the Director;
- at the request of the Council and/or the Director, provide supports to the Director;
- in collaboration with the Director, Alumni Relations, acts as a spokesperson for the MCAAC; and
- performs all other responsibilities and commitments outlined in the MCAA Council Director Position Description.
In the absence of the Chair, the Vice Chair acts as Interim Chair.
2. Specific Responsibilities of the Chair
The Chair sets a high standard for Council conduct by modeling, articulating and enforcing standards of conduct and performance found in MCAAC Advisory Guidelines, Terms of Reference, Belief Statement, and Charter. Without limiting the general responsibilities of the Chair described in Section 1 above, the Chair:
- Pre-Council Meeting Mechanics
- Schedules the number and timing of Council and Committee meetings each year so as to enable the Council to deal on a timely basis with all matters for which the Council is responsible and with which the Council as a whole chooses or is obliged to deal;
- Polls Council Members at least 10 days in advance of each meeting and seek their input as to possible agenda items;
- After consulting with the Director and the Executive Committee, establishes the agenda for each Council meeting with a view to bringing before the Council (i) matters with which the Council wishes or is obliged to deal, (ii) matters in respect of which management requires or wants Council input or feedback;
- Uses his/her best efforts to provide or to cause to be provided to the Council, within a reasonable timeframe in advance of each meeting (e.g. 7 days), all reasonably required and available information relating to each matter to be dealt with by the Council at that meeting; and
- Where, in the Chair's opinion, the subject matter and expected duration of a meeting or the particular circumstances of a member of the Council would so warrant, encourages a Member to participate in the meeting by means of telephone, teleconference, videoconference or other methodology by which Members participating in the meeting are able to speak to and be heard by each other;
- Conduct of Council Meetings
- Acts as the Chair of each Council meeting;
- Facilitates and mediates Council decisions;
- Facilitates and optimizes the constructive involvement and participation of all Members;
- Keeps the Mission, Vision, Values, Strategic Priorities, Belief Statement and identified strategic priorities/initiatives of the MCAAC foremost and uses them as a template/screen for all agendas and work plans;
- Conducts the business of each meeting in a manner which will result in the meeting's agenda being completed and dealt with effectively;
- Proposes the termination of discussion on any matter at a meeting when he/she is of the opinion that (i) the matter has been thoroughly discussed and that no new points of view or information are being presented; or (ii) the matter falls outside the scope of the agreed upon mandate of the Council.
- Attempts to achieve a consensus of Members on any matter discussed at a meeting in respect of which (i) the Council's decision, views or counsel has been requested or is required, and (ii) Members express conflicting positions, views or counsel and consensus is not available, the Chair will be guided by Robert's Rules of Order;
- Ensures that all Members who wish to address a matter at a meeting are afforded a reasonable opportunity to do so;
- Uses all reasonable effort to promote and support the Council's Guidelines and Charter;
- In any case where a Member has an interest or potential conflict in respect of a matter to be discussed at a meeting, attempts to arrange for the conflicted Member to excuse himself/herself from all or a portion of the discussion of that matter if the Chair is of the opinion that the discussion of that matter would probably be enhanced by the absence of the conflicted Member; and
- Calls special meetings of the Council when necessary.
- Council Composition and Education
In co-operation with rest of the Council, the Chair:
- assists in the identification of appropriate candidates to be considered for appointment to the Council;
- communicates on behalf of the Council with all proposed nominees for appointment to MCAAC to ensure that they are aware of the accountabilities stated in Council Guidelines, Position Descriptions and Terms of Reference prior to their official appointment;
- arranges for management of MCAAC to provide newly elected members with a comprehensive orientation and education program with respect to MCAAC and its businesses;
- designs and implements processes for evaluating the performances of the Council and individual Members;
- uses reasonable effort to cause the Council to be made aware on a timely basis of changes in best practices respecting the responsibilities of Council;
- seeks feedback on his/her performance as Chair; and
- Makes recommendations regarding the continuing education of Members.
- Miscellaneous Matters
- At the request of any member, meets or is available for discussion with that Member between meetings of the Council;
- Acts as Chair at all general and annual meetings of MCAAC;
- Coaches and mentor any identified successor Chair;
- Represents the Council at industry events, conferences, association meetings or other designated events;
- Communicates with any member as required regarding their performance as a Council Member (attendance, participation, conflict of interest, etc.)
- Performs other functions as the Council may specify from time to time.


text:
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Sales Manager
Savannah NOW - The Exchange: Networking: Newsmakers 07/27/02
www.savannahnow.com [cached]
Nona Story has returned to Village Park Realty, LLC, as sales manager of Woodbridge, a residential community by CraftBuilt Homes.Previously, Story had a successful 15-year real estate career with Tide Pointe and Cypress, as well as growing the Woodbridge name from the beginning.Story has lived in the area for 25 years and resides in Woodbridge.
Buckwalter Ventures, LLC~News & Archives
www.buckwaltercommercial.com [cached]
"There's no question growth is always good,"
Island Packet Online: Residential real estate robust
www.islandpacket.com [cached]
"We had a great summer," said Story, adding that the development sold double the homes this year as last year. Woodbridge is selling patio-style homes on quarter-acre lots for under $200,000.Homes on full-acre lots cost about $235,000, Story said. What are not selling well, according to Realtors, are homes in the million-dollar range.
Savannah NOW - The Exchange: Pulse: Bluffton's aorta 06/29/02
www.savannahnow.com [cached]
"There's no question growth is always good,"
CraftBuilt Homes Newsletter, Fall 2003, Associates
www.craftbuilthomes.com [cached]
Terri Story
Publix Super Markets, Inc.
Christopher Story
CommScope Inc
David Story
Calvary Baptist Church
Tyler Story
Act-On Software Inc

subset: commoncrawl


text:
Skip to comments.Wisconsin senators living day-to-day south of border..(Whine alert)
Posted on 02/21/2011 8:10:38 PM PST by GSP.FAN
Some senators left Wisconsin with little more than the clothes on their backs. Others came to Illinois equipped with an Urban Essentials pack: clothes, toiletries, cell phones, smart phones
(Excerpt) Read more at chicagotribune.com ...
Ah yes, the sympathy article from the Obama boot-lickers of the MSM.
Who's running that third-world backwater?
Cowards don't need much. Just a pair of fast running shoes and a safe place to hide.
The great liberal heroes continue their glorious battle against the evil, hatefilled taxpayers of Wisconsin.....
They'll be good for a month or two ~ Democrats don't ripen that fast in Winter!
I heard on the news that some moron in Egypt is ordering pizzas for the freeloading union thugs in Madison. Maybe the jerk should order some pizzas for these freeloading, 'RAT "senators".
If we just knew where they were, some nice WI FReepers would be glad to personally deliver some care packages. Heck, we'd even give them a free ride back to Madison!
Next is 0bama hiding out in a mosque.
To Wisconsin socialist liberals, a "patriot" to them is one who runs away, breaks the law by not showing up when the senate's in session, crosses state lines so as to have your own state's law enforcement not be able to bring you back to do your job, and sit around all day in a motel not being on the floor offering amendments and making your case even though you will not win the bill.
It's what Republicans have had to put up with anytime democrats are in power and we can't stop their bills. They are little crybaby socialist pussies who threw a temper tantrum because they can't legally win a battle and so they run away and hold the entire state hostage.
There is no way they will ever come across to most Wisconsinites as heroes. We'll get a bunch of non-fiscal bills passed in the meantime. They don't care anyway, they'd just be voting against them if they were here. Instead of passing 19-14 they will pass 19-0. Voter ID reform, here we come. Concealed carry, here we come.
Once they crossed the Cheddar Curtain, they should have been on their own. State credit cards canceled, state-paid mobile phones turned off, and access to their state-provided email and internet accounts blocked.
The Peoples Republik of Madistan: Birthplace of the Flee Party
It's all getting strange.
So if pizzas are being ordered for the flee-baggers then can't someone just follow the pizza delivery car and locate the runaways.
I thought this story was REALLY weird. They said morons for 5 different countries have been ordering pizzas but most are coming from some pinhead in Egypt. Like a greedy union thug can't afford his/her/its own pizza.
If you want to get REALLY disgusted....you'll click the link and read the WHOLE article...
Get your popcorns ready ... this is going to be fun, fun, fun.
What a lame excuse for an article! Like we're supposed to believe that these "fugitives" can't have their wives or flunkies simply FedEx them anything they need that that they're not willing to buy locally.
And what's the deal with roughing it in "survial mode" in Chicago, anyway? No stores? No restaurants? No five star hotels? I guess not. I really had no idea that living in Chicago or the rest of Illinois amounts to being in "survival mode". Guess they'll really be glad to get back to civilization when they leave Illinois and return to Wisconsin, hey?
"It's all getting strange."
The socialists have JUMPED THE SHARK.
I hereby coin the term 'ratfugees'. Pass it on to someone who knows how to use Twitter.
"Coggs has had to purchase underwear, socks and T-shirts...It's just roughing it"
And that's what makes America so great, people just rough it up.
Imagine having to go to a store and buy t-shirts or underwear???????????
I just heard on the news that the roaches are raising money. $300,000 from 1100 donors across the nation.
Well, did anyone think that Democrats would actually pay their own bills?
So grow up and go home.
Comrade Commissar Trumka should be willing to support them. Certainly he can afford to do so.
There was a link to a Wis. radio station online that I was listening to earlier & they said on there that most of them were back in Wis. over the weekend as the senate was not in session & they were moving about freely!
Can I haz big boom?
On the plus side, I'm sure he plans, after wearing the underwear for a few days, to donate it to the Salvation Army and then use the donation receipt to get a tax deduction - as did Bill Clinton.
Spot on!
Making Rat Policy Work By Hijacking the Democratic Process
Dems are a menace to our nation and damn near everyone living here.
What a bunch of clowns. It's nothing I haven't done 50 times when called out on a project that took longer than expected.
If they call sitting around in a hotel and occasionally going to a restaurant or store "roughing it", they are not worthy of leading the resourceful people of Wisconsin.
"South of the Border" ~ Gene Autry - 1939
It's time for Gov. Walker to announce that by a date certain if these rats are not back in their seats that their positions will be considered vacated and newly appointed reporesentatives will stand in until such time as elections can be held to replace them. Time to get tough!!
Let them stay there. The longer they do, the stupider they look.
I hope they are all wearing the same underwear they came with.
That IS taxable income !!
LOL - looks like a plan!
You're right Flyer - it's weird.
You're right.
I am about in tears. It must be so awful walking away from your job and still getting paid to sit in a hotel room or bar on the taxpayer dime.
Why, they have no clean clothes, no HD TVs, they forgot their swimsuits.....oh the horrors. And they are "doin' it" for the Kidzzzz.
Ping the cell phones, get a gps location, call in Dawg the Bounty Hunter and bring them back.
For the record, how does one ping a cell phone?
Probie McGee does it every Tuesday but I don't know how
Every cell phone has a unique electronic serial number,the cell tower reads the number, now that smart phones have GPS, they can find the location without triangulation.
———Every cell phone has a unique electronic serial number-——
Granted, but how does one ping or access the GPS data
They used to use consecutive towers to track or triangulate the position, now you are also logged into the GPS system, trust me if they wanted these guys,they could have them within an hour.
Disclaimer: Opinions posted on Free Republic are those of the individual posters and do not necessarily represent the opinion of Free Republic or its management. All materials posted herein are protected by copyright law and the exemption for fair use of copyrighted works.


text:
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Don't stress... It's free and easy to setup.
The Southeast Lauderdale Tigers girls basketball team won Thursday's away playoff game against Newton by a score of 63-52.
(February 9, 2012: Newton, MS 39345) Southeast Lauderdale Tigers (Meridian, MS) backers were in high spirits Thursday as they witnessed their basketball squad thwart the host Newton Tigers (Newton, MS), 63-52 in a non-league bout.
With the win, Southeast Lauderdale upgrades its record to 22-7 on the season.


text:
Maritime Today
The Maritime Industry's original and most viewed E-News Service
Nick Brown has been appointed Bureau Veritas' new Communications Director, Marine & Offshore Division, the classification society announced.
Brown will take up the post from November 2,
International accountant and shipping adviser Moore Stephens says the shipping industry must adopt a transparent, proactive approach to corporate governance or
Cash-strapped Hanjin Shipping Co. sources say that the negotiations with tonnage providers for lower rates are undergoing, but wouldn't say much else.
According to Korea Herald, the country's No.
China and Russia will hold "routine" naval drills in the South China Sea in September, China's defence ministry spokesman Yang Yujun told a news conference on Thursday.
India has inked a deal with the US defence and aerospace giant Boeing to procure four more Poseidon-8I (P-8I) long-range surveillance and anti-submarine warfare
1776 - During the American Revolution, the Continental brig, Reprisal, commanded by Capt. Lambert Wickes, transports the newly appointed commercial and naval agent, William Bingham, to Martinique.


text:
|Publication number
|Publication type
|Publication date
|Mar 16, 1965
|Filing date
|Jun 8, 1959
|Priority date
|Jun 8, 1959
|Also published as
|Publication number
|Bowers Albert
|Original Assignee
|Syntex Corp
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (2), Referenced by (5), Classifications (43)
|External Links: USPTO, USPTO Assignment, Espacenet
United States Patent Ofi ice 3,173,914 Patented Mar. 16, 1965 3,173,914 5,6-D1FLUOR0 STERGHDS AND PROCES FQR THE PREPARATIGN TEEREOF Albert Bowers, Mexico City, Mexico, assignor, by mesne assignments, to Syntax Corporation, a corporation of Panama No Drawing. Filed .lune 8, 1959, Ser. No. 818,505 20 Ciaims. (Cl. 260-23955) The present invention relates to a novel method for the production of fiuorinated organic compounds and to certain novel compounds so prepare-d. More particularly, the present invention relates to a novel process for the production of fluorinated aliphatic, cyclic, and cyclic aliphatic organic compounds.
The production of monofluoro alkanes by treatment of hydrocarbon olefins with hydrofluoric acid is a Well known process; the reaction is usually carried out without a catalyst and at wide temperature ranges. Ethyl fluoride in good yields may be prepared in this way. With longer, branched chain, or-cyclic olefins, however, this reaction is complicated by the fact that monofiuoro alkanes, especially secondary and tertiary fluorides, are diificult to purity, and that small amounts of Water or acids, particularly hydrofluoric acid will initiate decomposition and isomerization. An alternative method of introducing fluorine into olefinic hydrocarbons, especially of olefinic cyclopentanophenanthrene derivatives having double bond between carbon C5 and C-6 of the nucleus forming useful fi-fluoro cyclopentanophenanthrene derivatives has been described for example in US. Patents Nos. 2,838,- 492 to 2,838,502 and others. This method involves formotion of the corresponding 5,6-oxido derivatives, separation of the 5a,6e-epoxides from the 55,6;8-isomer, and finally opening of the 50,6ct-OXidO derivative with hydrofluoric acid. It will be apparent that the present method, which is also suitable for introducing fluorine atom at carbon C-6 of cyclopentanophenanthrene derivatives involves only one step, as compared to three steps of the above cited patents, and can be hence generally achieved at higher yields and lower cost.
In accordance with the present invention, the surprising discovery has been made that hydrofluoric acid, in the presence of a positive halogen ion (halogen or halo wherever herein used means other than fluorine or fluoro), will react with hydrocarbon olefins to produce stable fluoro-halo derivatives. It has been further discovered, in accordance with the present invention, that catalytic dehalogenation of fluoro-halo compounds will give fluorinated alkanes in high yields.
There has been further provided therefore a novel process, involving novel intermediates, for the production of fluorinated compounds heretofore not accessible.
In practicing the novel process olefinic hydrocarbons are treated with hydrofluoric acid in the presence of amides or imides, N-halogenated with chlorine, bromine or iodine acting as a source of positive halogen ion; the reaction may be further carried out, to obtain higher yields in presence of a proton acceptor; suitable proton acceptors are organic bases capable of accepting protons, which do not form insoluble complexes, or react with either of the reactants; such proton acceptors are preferably selected from the class consisting of hydrocarbon others or ketones.
The reaction of the present invention may be exemplified generally by the following equation:
In the above equation X represents a halogen atom of atomic weight from 35 to 130 i.e. chlorine, brominev or iodine and R, R R and R stand for hydrogen or sepa rately or together a hydrocarbon of less than 20 carbon atoms, straight or branched chain aliphatic, cyclic or cyclic aliphatic, or an aryl group of less than 11 carbon atoms; the ethylenic double bond may be further a part of a cyclic or cyclic-aliphatic hydrocarbon of less than 40 carbon atoms. Typical examples of compounds rep resented by the above equation are olefins such as ethylene, l-butene, Z-pentene, S methyI-I-butene, 3,3-dimethyll-butene, l-undecene, cyclobutene, cyclohexene, l-n-propyl-cycloheX-1-ene, further members of the monoterpene, sesquiterpene, diterpene or triterpene compounds, such as limonene, menthene, a-santalene, abietic acid, lupeol and lanosterol and cyclopentanophenanthrene derivatives such as cholesterol, A -androsten-3fi,17 B-diol, A -pregnen- BB-ol-ZO-one, dianhydrostrophantidin, episterin, fucosterin, ,G-sitosterol, diosgenin and correllogenin.
Typical compounds within the above definitions which are especially suitable for the novel reaction to give highly useful products are those which may be illustrated by the following formulas:
In the above formula Z stands for H at keto group, 115 or lla-hydroxyl; X represents a hydrogen or a halogen atom of an atomic weight between 19 and i.e. fluorine, chlorine or bromine; Y represents a keto or fi-hydroxyl group, which may be further substituted in the a-position with a saturated hydrocarbon of less than six carbon atoms, such as methyl or ethyl or a pregnan side chain, characteristic for example of progesterone, l7a-hydroxy progesterone or cortisone; R represents a hydroxyl or ethylenedioxy group; R represents a hydrogen, a hydroxyl group or a methyl group; R represents a hydroxyl or hydrogen; R a hydroxyl or a ketone; R a hydroxyl or an alkoxy group such as methoxy or ethoXy and R may be a hydrogen or a methyl group; the alcoholic groups in compounds as above set forth may be further in the form of esters formed with hydrocarbon car- 'boxylic acids of less than 12 carbon atoms, either straight or branched chain aliphatic, cyclic, or cyclic aliphatic; typical examples of such esters are the acetate, propionate,
3 butyrate, benzoate, cyclopentylpropionate or trimethylacetate.
The novel process therefor leads to the production ofnovel intermediates of the following formula:
COCH2OR15 CO-OHgOR" 4 ORlfi and R represents hydrogen or a hydrocarbon carboxylic acyl group of up to 12 carbon atoms as conventional in steroids such as acetate, propionate, cyclopentylpropionate or benzoate, and R represents hydrogen, lower alkyl, lower alkenyl or lower alkinyl.
It will be also apparent, that the novel process may be practiced upon the corresponding 19-nor compounds of the above formulas, i.e. those lacking the angular methyl group attached to carbon C-10.
Typical compounds within the above definitions which may be subjected to the novel reaction are A -androsten- 3,8-ol-17-one, the dia'cetat'e of 17a-methy1-A -androsten- 35,17 8-di0l, 3-ethylenedioxy-17a-methyl-9a-fluoro-A -androsten-17B-ol-11-one, A -pregnen 3B-ol-20-one, the r17- acetate of A -pregnen-3B,17u diol-2O-one, 3-ethylenedioxy- A -pregnen-l7u-ol-20-one, 9a-chlorO-M-pregnen-3B,17w diol-11,20-dione, 3-ethylenedioXy-M-pregnen-17a,21-diol- 11,20-dione, 16,21-diacetate of 9a-fluoro-3-ethylenedioxy- A -pregnen-1 1B, 1 6a, 170:,21-t6t170l-20-01l6, A -pregnen-3B- ol-20-one, the acetate of A -allo-pregnen-3fi-ol-11,20- dione and the 3,2l-diacetate of A -pregnen-3fi,21-diol-20- one, A -dehydro estrone, the methyl ether of A -dehydro estrone, the acetate of A -dehydro estradiol, l-methyl estrone and 1,2,17-trimethyl A -dehydro estradiol.
The novel reaction, as hereinafter described, is further efiective upon the double bonds of the perhydrophenanthrene molecule, as above set forth, which are between carbon C-1 and C-2, C-2 and C-3, C-3 and C-4, C4 and C-5, C-5 and C-10, C7 and C-8, C9 and C-ll, C-8 and C-9, C 8 and C-14, C-11 and C-l2, C-l3 and C-14, 0-13 and C-17, C-14 and C-15, (3-17 and 'C20 and C-20 and C21, as well as upon conjugated double bonds; typical examples of compounds within the above definition are A -androsten-l7/3-ol-3-one, M -pregnen-3B-ol-20-one, the 21-acetate of 3-ethylenedioxy A -pregnadien-l7m,21-diol-20-o'ne, the ZI-acetate of A -pregnadi'en-17a,21 di-ol 3,11,20-trione, A -pregnadien-17a-ol-3,20-dione, the 17,2l-diacetate of A -pregnadien-l7a,2'1-diol-3,ZO-dione, and the 3,l7-diacetate of A -pregnadien-3,l7a-diol-20-one. The novel process is further applicable to olefinic hydrocarbons, having in the rest of the molecule groups which are susceptible to the attack of hydrofluoric acid under the normal conditions of addition to an olefinic double bond, that is in absence of a positive halogen ion as above defined. Such groups may include for example B 'y-unsaturated ketones, which are known to rearrange to cap-unsaturated ketones with strong acids, epoxide groups, which are known to give the corresponding fluorohydrins by action of hydrofluoric acid, or esters which are known to hydrolyze to the free alcohols with mineral acids. Thus for example treatment of 21-acetate of A -pregnadien-3fi,17,21-tri01-20- one with hydrofluoric acid and N-halo amide or imide underthe conditions as below described in detail, folfollowed by isolation gives 2l-acetate of A 5oc-hal0- 6B-fluoro-pregnen-3fi,-l7a,21-triol-20-one. Oxidation of thiscompound in a known manner,- as for example with chromic acid in acetone and treatment of the ketone with for example dry hydrogen chloride in acetic acid gives 21-acetate of 6u-fluoro-A -pregnadierhl7u,2l-diol- 3,20-dione, a compound which in turn may be converted in a known manner by treatment with for example hypobromous acid, sodium acetate and hydrogen fluoride, to the corresponding 6a,9oc-difiuoro-cortisone, cortical hormone of known therapeutic efficacy.
The novel process therefore is especially suitable for the preparation of novel Sa-haIo-QB-fluoro steroids of androstane and pregnan series, which are useful intermediates for the production of 6-fiuoro androstan and pregnan derivatives of known therapeutic use, as disclosed for example in US. Patents Nos. 2,838,492 to 2,838,502, as well as others; the novel process is likewise suitable for the production of 6B-flll0lO-7oc-hfll0 compounds which are useful intermediates (by elimination of the 7a-halo group as herein described) for preparation of corresponding 6-fiuoro-A -dehydro androstan and pregn-an derivatives. These A compounds of the androstane series have an enhanced anabolic-androgenic ratio, of the 21-desoxy pregnane type are progestational and of the 2l-hydroxy type are anti-inflammatory and cortical. The novel luhalo-2,8-fluoro-, Sa-haloSfi-fluoro 9oz-h2ll0-l1fi-flll0lO-, 10,8-halo-5oz-fiuoro-, ll/S fiuoro-lM-halo, 17fi-fiuoro-20- halo, 16,8-fluoro-17a-halo, and 7e-halo-8 3-fiuoro cyclopentanophenanthrene derivatives specifically described hereinafter are useful intermediates for the production of the corresponding novel and therapeutically useful compounds, Z-fiuoro-N-dehydrm, 8/3-fiuoro-, 9B-fiuoro-, 1113- fluoro-, -fiuoro-, and 7,8-fluoro 'cyclopentanophenanthrene derivatives by elimination of the halo group as herein described. These novel compounds exhibit androgenic, anti-androgenic, catabolic, eosinophilic, antiinilammatory, progestational and myotropic activity and are also active in suppressing the activity of the pituitary gland. pregnenderivatives are useful intermediates for the production of known therapeutically useful 4-fiu0ro-M-androsten and pregnen compounds.
The known 6-fluoro-A -3-keto steroid derivatives and novel intermediates of the androsten and pregnen series may be prepared from A -compounds in accordance with the present invention as exemplified in the equation below:
lij gj- V ZQj-{U 0: q a (as The novel 5a-halo-4 6-fiuoro androstan and In the above formula R X, X Z and Y represent the same groups as above set forth.
In practicing the novel process as above shown, treatment of A -3-lteto steroids of androstadien and pregnadien series with hydrofluoric acid and N-halogenated hydrocarbon amide or imidie, preferably in presence of hydrocarbon ether or ketone, gives 65-fiuoro-7a-halo (bromo, chloro or iodo) A -3-keto steroid compounds; these compounds may be treated with a reducing agent as for example with hydrogen in presence of suitable catalyst, or with magnesium-iodide mixture and then with Water, to effect the replacement of the 7a-halogen for hydrogen. The 6,8-fluoro compounds thus obtained may be further treated in known manner with agents capable to effect isomerization, such as for example with hydrogen chloride in acetic acid to give the corresponding 60:- fiuoro derivatives, useful therapeutic agents of known pharmacological potency.
The novel process therefore leads to the production of novel intermediates of the following formula:
In the above formula X, Z and X represent the same groups as heretofore, R represents hydroxyl, keto or ethylenedioxy, R represents hydrogen, hydroxyl or methyl and R represents =0,
ORH COCH3 CO-CH3 C O-GIEI OR R H on B o o-cmo R15 and R represents hydrogen or a hydrocarbon carboxylic acyl group of up to 12 carbon atoms as conventional in steroids such as acetate, propionate, cyclopentylpropionate r benzoate, and R represents hydrogen, lower alkyl, lower alkenyl or lower alkinyl.
Alternatively, it has been discovered in accordance with the present invention, that treatment of the 6fl-fluo-ro-7ahalo steroids with lithium chloride or calcium carbonate in dimethyl formamide at elevated temperatures, preferably around the boiling point of the solvent used, eliminates preferentially the 7u-halo atom and there are obtained 6-fiuoro-n -dehydro steroids, which are likewise known useful therapeutic agents.
Typical useful compounds within the above definition are for example 6a-fiu0ro-testosterone, 6e-fiuoro-progesterone, acetate of 6u-fiuoro-17whydroxy progesterone, acetate of 6u-fiuoro cortisone, 60:,9a-(llfit101'0 hydrocortisone, l6u-hydroxy-6oa9a-difluoro cortisone and hydrocortisone and l6u-methyl-6a,9m-difluoro cortisone and hydrocortisone, acetate of fi-fiuoro-n -de'hydro-l7u-hydroxy progesterone 6-iluoro-zl -dehydro-l'7u-hydroxy progesterone, 6-fiuoro-A -dehydro cortisone and 6, (X-difiuO1'O-160L- hydroxy and lde-methyl-cortisone.
To carry out the novel reaction there are used as a source of positive halogen ion, N-halogenated hydrocarbon amides or imides obtained in a known manner by treating, with hypohalous acids or elemental halogen, amides or imides derived from hydrocarbon monoor dicarboxylic acids of less than 20 carbon atoms.
6 The N-halogenated amides or imides within the above definition may be illustrated by the following formulas:
In the above formula X represents halogen having atomic weight between 35 and and R and R represent a saturated or unsaturated hydrocarbon of less than 20 carbon atoms, straight or branched chain aliphatic, cyclic, or cyclic aliphatic; typical examples of such amide or irnide are acetarnide, propionamide, n-butyramide, isobutyr-am-ide, palmitamide, succinimide, phthalimide, benzamide and p-toluenamide, N-halogenated by chlorine, bromine or iodine.
The proton acceptor, as above set forth, is prefer-ably selected from hydrocarbon ethers or ketones. The ethers may be derived from saturated or unsaturated hydrocarbons either straight or branched chain aliphatic, cyclic, or cyclic aliphatic of less than 9 carbon atoms, such as for example dioxane, furane, tetrahydrofurane, diethyl ether, methyl n-butyl ether, di-n-butyl ether, diisoamyl ether, di-n-hexyl ether, ethylene glycol dimethyl ether and diphenyl ether. The ketones may be derived from saturated or unsaturated hydrocarbons either straight or branched chain aliphatic, cyclic or cyclic aliphatic of less than 16 carbon atoms, such as for example methyl ethyl ketone, acetone, diethylketone, dii-sopropylketone, acetyl acetone, cyclo-hexanone, benzophenone, and also diketones such as quinone, anthraquinone and 1,4-naphtoquinone.
In practicing the process of the present invention, hydrofluoric acid, 1 to mols, but preferably about 30 mols, and preferably in form of anhydrous hydrofluoric acid, is optionally mixed with an hydrocarbon ether or ketone as above defined, either added alone or dissolved in an inert organic solvent; There is used between 0.1 to 2 mols of the ether or ketone, but preferably there is used approximately 0.5 mol per one mole of the hydrofluoric acid used. The mixture is then cooled to below 0 C., preferably between l5 to 80 C. and to the cooled mixture is added approximately 1.0 mol of the compound to be fluorinated, preferably dissolved in an inert organic solvent. Suitable solvents may be selected from saturated liquid hydrocarbons, cyclic, aliphatic or cyclic aliphatic, such as hexane, octane or cyclohexane, further aromatic hydrocarbons, such as benzene or toluene or preferably halogenated hydrocarbons such as for example chloroform, or methylene chloride. Finally, to this mixture is added between 0.5 to 1.5 molar equivalents, but preferably approximately one molar equivalent of N-halogenated amide or i-mide. The reaction mixture is then allowed to react at temperatures below 0 C. for approximately between 15 minutes to 3 hours and the iluorinated-halogenated product is isolated in a conventional manner. It has been found that the reaction may be also carried at temperatures higher than 0 C.; in this case, the reaction is carried out preferably under pressure.
The isolated halogenated-fiuorinated product is then dissolved in an organic solvent, such as for example lower aliphatic alcohol, ester of lower aliphatic alcohol with lower aliphatic acid, further lower aliphatic hydrocarbon and lower aliphatic carboxylic acid. Typical examples of such solvents are methyl alcohol, ethyl alcohol and pro-pyl alcohol, ethyl acetate, arnyl acetate and butyl propion-atc, hexane and octane, further formic, acetic and propionic acid. To this solution is then added a catalyst, between 0.1 to 5 times the weight of the halogenated-fluorinated product, commonly used in hydrogenation processes; such catalyst is selected preferably from the metals forming the eighth group in the periodic table, such as for example nickel, palladium, ruthenium and platinum; the catalyst may be employed either in the metallic form or in form of its oxides, deposited perhaps on a suitable carrier, such as carbon, calcium carbonate or barium sulphate. 'The reaction mixture is then maintained at between to 45 0., but preferably at around 25 (3., while stirring, and under an atmosphere of hydrogen, for approximately between 0.5 to 8 hours till the exchange of hydrogen for halogen is complete. 7
It has been further discovered in accordance with the present process, that the dehalogenation above described, can be carried out using a reducing agent, preferably chromous chloride. In practicing the process as above set forth, the halogenatedfluorinated product is dissolved in a water miscible solvent, such as a lower aliphatic carboxylic acid, or lower aliphatic ketone as for example acetic acid or acetone, and an aqueous solution of chromous chloride, preferably about 1.5 mols, is added. The solution is stirred at about 25 for approximately /2 hour, when the exchange of halogen for hydrogen is completed, and the fluorinated product is then isolated. In cases where, in the halo fiuoro compounds, the halogen stands in fl-position to a functionally derived, or protected ketogroup, such as for example an alcohol or a ketonic derivative such as 'ketal, the ketonic function is first regenerated in the known manner, as for example by oxidation with chromic acid, or by treatment with an inorganic acid. The fl-halogen is then eliminated by treatment with mineral acids in suitable organic solvent (of. Barton et al., J.A.C.S., 1066 (1950)). Such methods involve for example treatment of the halo-fluoro ketone with hydrochloric acid, or with alkali metal salts of lower aliphatic carboxylic acids, preferably sodium' acetate; suitable solvents for such reaction are lower aliphatic carboxylic acids, lower aliphatic alcohols, ketones ,or halogenated hydrocarbons; typical examples of such solvents are acetic and propionic acid, methyl, ethyl and butyl alcohol, acetone and methyl propyl ketone, chloroform and methylene-chloride.
It has been further discovered in accordance with the present invention, that reacting'the fiuoro-halo (bromo for example) compounds as above set forth with magnesium metal, preferably in finely divided form and in presence of iodine, there is formed the corresponding magnesium halide (bromide for example) compound, which, upon addition of water is converted into the corresponding fluoro derivative.
This process if preferably carried out in an inert anhydrous organic solvent selected from hydrocarbon others as above set forth, such as for example diethyl ether, dioxane and tetrahydrofurane.
In practicing the process of halogen elimination as above set forth, the corresponding halo-fiuoro compound is dissolved forexample in dry ether; finely divided magnesium, about 0.8 to 3 mols, but preferably about 1.5 moles and iodine, about 0.005 to 0.5 mole, but preferably about 0.1 mole, are treated for about 5 minutes to about 150. This mixture is then cooled under anhydrous conditions and is added to the ethereal solution of the halo-fluoro compound. This mixture is stirred first. at room temperature for between 2 to 15 minutes and may be further stirred for additional 5 to about 15 minutes, while heating to refluxing if the formation of the magnesium halide should be incomplete. The mix- 8 ture is then cooled to room temperature, water is added, and the solution is again stirred for about 10 to minutes.
Additional water may then be added to facilitate the separation of the organic layer and the fiuorinated compound may then be isolated and purified in a conventional manner, as for example by crystallization.
The novel process of the present invention as described is suitable for the preparation of monofiuorinatcd compounds by addition of the fluorine atom to a single olefinic double bond; it is clear, however, that if it is desired to introduce several fluorine atoms into compounds having two or more olefinic double bonds, there has to be used two or several times moreof the principal reactants,.su'ch as hydrofluoric acid and the halogenated amide or imide, depending on the number of fluorine atoms to be introduced and upon the number of the double bonds present in the molecule.
The following specific examples serve to illustrate but are not intended to limit the present invention. The degrees are indictaed in centigrade degrees.
EXAMPLE I To a mixture of 5 g. of hydrofluoric acid and 8.8 g. of tetrahydofurane, cooled to C. was added a cold solution of 1 g. of cyclohexene, dissolved in 50 cc. of methylene dichloride, and 1.05 molar equivalents of N-br omo-acetamide added in portions, while stirring. The reaction mixture was maintained at 80 C. for 1 hour and then at 0 C. for an additional hour; it was then poured into cold water, containing suiiicient sodium carbonate to neutralize the excess of hydrofluoric acid, the organic layer was separated, washed. with water, dried over sodium sulfate and the solvent was evaporated in vacuo maintaining the bath temperature at 5055 C.; the distillation residue consisted of l-bromo-Z-fluoro cyclohexane, i
To the above compound, dissolvedin 50 cc. of acetone, there was added 2 g. of Raney nickel and the suspension was stirred at room temperature for 2 /2 hours; the catalyst was then removed by filtration under nitrogen atmosphere and the resulting monofiuoro-cyclohexane was purified by'distillation under reduced pressure.
EXAMPLE II By the same method as described in Example I, but substituting tetrahydrofurane by dioxane and N-bromoacetimide by N-iodo succinirnide, there was obtained monofluorocyclohexane in essentially the same yields.
EXAMPLE III 2 g. of 1-bromo-2-fiuoro cyclohexane, obtained in accordance with Example I, was dissolved in 40 cc of ethyl acetate, 350 mg. of palladium on charcoal (5%) was added, and the mixture was hydrogenated at atmospheric pressure and room temperature till the uptake of 1 mol of hydrogen was completed, which took approximately 3 /2 hours. The catalyst was then removed by filtration and the solvent was removed by distillation under reduced pressure. The resulting monofluorocyclohexane was identical with the compound prepared in accordance with Example I.
EXAMPLE IV 2 g. of cyclohexen, 50 cc. of chloroform and 12 g. of hydrofluoric acid were mixed, cooled to -65 and divided into eight portions. To each portion was then added 0.5 mols of a proton acceptor and 1.1 mols of the N-halogenated amide or imide, as indicated. The intermediate compounds formed were isolated as indicated in Table I. a
EXAMPLE V 2 g. of A -androsten-3B,l'i'fi-diol and 50 cc. of solvent, as indicated in Table II, were mixed, divided into six portions, 1.1 mol of N-bromosuccinimide was added to each portion and the reaction was carried out in presence or absence of a proton acceptor and at temperatures as indicated. At the end of the reaction the product was isolated as described in Example I and the yields of 5abromo-Gfl-iiuoro-androstan-Efi,l7fi-diol were compared as shown in Table II.
Table II Tempcr- Time Yield, Solvent Proton acceptor ature, (hrs) percent degrees Methylenechloride. Tetrahydrofurane..- 70 1 80 Do None 0 1% 35 Tetrahydroiuranmn 65 1% 78 do O 1 46 0 1 25 15 EXAMPLE V1 1.5 g. of octene-l was dissolved in 40 cc. of carbon tetrachloride, 10 g. of anhydrous hydrofluoric acid and 16 g. of tetrabydrofurane was added and the mixture was cooled to between -65 to 70 and was maintained at this temperature throughout the reaction. 1.1 molar equivalents of N-oromosuccinimide were added in portion and the reaction mixture was then maintained at the same temperature for about 1 hour. Following the same isolation procedure as described in Example I there was isolated l-bromo-Z-fluoro octane.
Catalytic hydrogenation of this compound with palladium on carbon as described in Example III gave, after purification by distillation, Z-fiuoro octane.
Following, the same method as described above there were prepared the halo-fluoro and finally iluoro compounds as outlined in Table III.
Table III 1% EXAMPLE VII 1 g. of cyclophexene, dissolved in ml. of chloroform, was added to 4 g. of hydrofluoric acid, the mixture was cooled to -65", and then there was added 1.1 molar equivalents of N-bromoacetamide in portions, while stirring. The reaction mixture was maintained at 65 C. for 1 /2 hours, then at 0 to +5 C. for an additional hour and was finally worked in the same manner as described in Example I. The yield of l-brorno-Z-fiuorocyclohexane was only about 40% as compared to yields obtained in Example 1.
EXAMPLE VHI By the same method, as described in Example I, but substituting the 8.8 g. of tetrahydrofurane by 4.2 g. of fluorenone and cyclohexene by hexen S-oic acid there was obtained 5-fiuoro-6-bromo hexanoic acid. 1 g. of the above acid, dissolved in ml. of methanol, and 200 mg. of palladium on carbon (5%) was maintained under hydrogen atmosphere, While stirring at room temperature until there was absorbed 1 molar equivalent of hydrogen; the catalyst was renewed by filtration, the solvent removed by distillation under reduced pressure; thus was obtained crude S-fiuoro hexanoic acid, which was purified by chromatography in silica gel.
EXAMPLE IX By the same method as described in Example I, but substituting the N-brornoacetamide by N-bromosuccinimide, methylene chloride by octane, and cyclohexane by the methyl ester of hcxen-S-oic acid, there was obtained finally the methyl ester of S-fluoro-hexanoic acid.
EXAMPLE X By the same method of described in Example I, by reacting 1 g. of M-pregnen-Bgi-ol-ZO-one with hydrofluoric acid and N- bromoacetamide there was obtained 950 mg. of 5a-bromo-6,3-fiuoro-pregnan-3,8-ol-20-one. The above compound, dissolved in 50 cc. of acetone, was cooled to 0 and was then treated with 1.1 mol of 8N chromic acid (prepared from chromium trioxide and aqueous sulfuric acid) under nitrogen atmosphere while stirring, and maintaining the temperature at 0 C. The reaction mixture was stirred for additional 5 minutes at i0 C., was diluted with water, the precipitate was collected by filtration, washed with water till neutrality and dried; thus was obtained crude 5 z-bromo-6,B-fluoropregnan-3,ZO-dione.
The above compound, dissolved in 35 cc. of glacial acetic acid, was treated with dry hydrogen chloride gas for four hours maintaining the temperature at 15 C.; the solution was then poured into cold water, the precipitate was filtered, washed With water, dried and crystallized from acetone-hexane; the 6a-flu0ro progesterone, thus obtained, was identical with an authentic specimen.
Starting Material Intermediate compound Final compound Hexene-l 3 meth yi-butenc-l 2,3-dimcthyl-2-butene.
Citronellol 2,G-dimethyl-octJ-en--one a-Pinene- 7 T 162,17or-8Q0Xitl0 n neostcrol n (H) -choleste n -pregnadien- 1 1 EXAMPLE I 0.5 g. of a-bromo-65-fiuoro-pregnan-3,20-dione was 7 dissolved in 25 cc. of methanol; 1 g. of anhydrous sodium acetate was added and the mixture was refluxed for 3 hours; it was then cooled, water was added and the precipitate filtered, washed and dried.
Crystallization from ether gave Gfi-fluoro progesterone, identical to an authentic specimen.
EXAMPLE XII Treatment of 5u-bromo-613-fluoro-pregnan-3,8-ol-20-one, obtained as described in the above example, with Raney nickel or palladium on charcoal as described in Example III gave in almost the same yields 6B-fluoro-all0pregnan- 3,8-ol-20-one.
EXAMPLE XIII By the same method as described in Example I but using the hydrogenation method, in presence of 200 mg. of ammonium acetate per 1g. of compound, as described in Example Ill and starting from the materials as indicated, there were obtained the following intermediates and final compounds.
12 g. of anhydrous sodium sulfate. Filtration and removal of the solvent under vacuum aiforded 16/3-fluoro-A pregnen-3/3,21-diol-1l-one, purified by crystallization from acetone-hexane.
The above compound was dissolved in 15 cc. of pyridine containing 2 cc. of acetic anhydride and the mixture was kept at room'temperature for 16 hours. Addition of ice water and filtration aiforded 16,8-fiuoro-A -pregnen- 35,21-diol-11-one diacetate.
EXAMPLE XV Starting Compound Intermediate Final Compound 21-acetate of A -pregnadien-17a, 21-diol- 3,11,-20-trione.
A -androstadien-l7fi-ol-3-one one.
one. androstendm-ol-s-one. l7a-ethyl-A -andrcstadien-l7B-ol-3-one andr0sten-176-ol-3-one. 17-aeetate of Qa-finoroh -pregnadien- 11B, 17a-diol-3, ZO-dione. 2l-acetate of A -pregnadiem17a, 21-
diol-3, ZO-dione. 16fl-rnethyl-A -nor-androsten-3B, 17/3- diol. androstan-3f), 17Bdiol. 17,21-diacetate of A -pregnadien-l7a,
21-diol-3, 20-dione. N-cholestenoL; A -3oz, 12a-dihydroxy-cholenic acid 2l-trimethy1 acetate of A (11) pregnadien-17a-2Ldiol-3, 20-dione.
cholanic acid.
The acetate of A -allopregnen-wel-ll,
A -pregnen-3B-0l-2O-one A -pregnadien-3, ZO-dione allopregnan-35-ol-l1, 20-(11 drone.
ll-trimethyl-acetate of 9a-brorno-11,8- fluoro-A pregnen-Ha, 21-diol-3, 20-
I .01. 17,21-diacetate of SB-fiuoro-N-pregnen-IM,
21-diol-3, 20-dione. 8fltluoro-cholestanol. 8,3-rluoro-3a, IZa-dihydroxycholamc acid.
21-trimethyl acetate of llfi-fiuoro-A pregnen-lm, 2l-diol-3, 20-dione.
EXAMPLE XIV 1.0 g. of 16;8-fiuoro-17a-bromoallopregnan-3,B-ol-l1,20- dione acetate produced in accordance with the method of Example I by treatment of A -allopregnene-35-ol-11,20- dione acetate with hydrofluoric acid and N-bromo-acetamide in methylene dichloride solution in the presence of tetrahydrofurane, was dissolved in cc. of acetic acid. To this solution at 15-20 was added one drop of a 7 N hydrogen bromide solution in acetic acid and then a solution of 240 mg. of bromine in 5 cc. of acetic acid. After stirring at 20 for 2 hours, addition of water and filtration gave 16fi-fluoro-17a,21-dibromo-allopregnan-3[3-ol-ll,20-dione acetate which was purified by crystallization from methylene dichloride-hexane.
1.0 g. of the above compound, was dissolved in cc. of absolute methanol containing 570 mg. sodium and the solution was kept at room temperature for 16 hours. After neutralizing with acetic acid the solution was evaporated to a small volume. It was then poured into water, the precipitate was collected by filtration and the resulting crude l6fl-fluoro-2l-carbomethox -A -pregnen-3fl-ol- 11-one was purified by chromatography over alumina.
The above compound was dissolved in cc. of ether and the solution was added over 10 minutes to a stirred suspension of 250 mg. of lithium aluminum hydride in 50 cc. of ether. After a further 10 minutes at room temperature the excess of reagent was destroyed by the addition of ethyl acetate. A saturated solution of sodium sulfate (5 cc.) was then added followed by the addition of 25 To a. solution of the above compound (1 g. in 50 cc. of acetone) was added 8 N chromic acid solution (1.05 equivalents) while maintaining the temperature at :0". The solution was kept at the same temperature while stirring for additional 5 minutes, water was added and the precipitate was removed by filtration. Crystallization from ethyl acetate hexane afforded 16,8-fl-uoroallopregnan- 3,8,17a,21-trio1-11,20-dione-3 ,2 l-diacetate.
EXAMPLE XVI 250 mg. of potassium hydroxide was added to a solu tion of 1 g. of 16,8-fluoroallopregnan-3fi,l7a,2l-triol-l1, 20-dione-3,21-diacetate in cc. of methanol at 0 in an atmosphere of nitrogen. After stirring at 0 for 1 hour the solution was neutralized with acetic acid. Ad-
dition of water precipitated l6f3-fluoroallopregnan-llfi,17oz, 21-triol-11,20-dione. Acetylation of this product by treating a solution in pyridine with 1.05 equivalents of acetic anhydride at 0 for 24 hours gave 16,8-fiuoro-allopregnan-3fi,17a,21-triol-1 1,20-dione monoacetate.
EXAMPLE XVII Oxidation of the product obtained in the preceding example with chromic acid in acetone according to the method described in Example XV led to l6fi-tluoroallopregnan-17a,21-dio1-3,1 1,20-trione 21-acetate.
EXAMPLE XVIII 2 milli mols of bromine in 5 cc. of acetic acid was added to a solution of 16,8-tluoroallopregnan-17a,21-di0l- 3,11,20-trione (1 mol) in 30 cc. of acetic acid at 10 over 10 minute period. The uptake of the bromine was very rapid. After a further 5 minutes ice water was added and the precipitated 1Gdtluoro-ZA-dibromoallopregnan l7ot,2l diol-3,ll,2i)-trione ill-acetate was removed by filtration. The crude dibromo compound was dried at room temperature in vacuo. it was then dissolved in dimethyl acetamidc (20 cc.) and added over 10 minutes to a suspension of 500 mg. of calcium carbonate in boiling dimethyl acetamide (25 cc.). reflux for a further minutes the calcium carbonate was removed by filtration. Addition of water and filtration gave lfifi-fiuoroprednisone acetate purified by chromatography over alumina and crystallization from acetone.
After heating under 10 EXAMPLE XIX By the same method as described in Example X there were prepared the intermediate and final compounds as indicated in Table IV.
By the same methods as described in Example XIX and XX there were obtained, starting from the appropriate A dehydro derivatives the following intermediate and final comp ete.
1 4 EXAMPLE XXI 1 g. of the acetate of 6,8-fiuoro-7a-bromo-testosterone, obtained as described above, was dissolved in 50 cc. of methanol, ammonium acetate, 200 mg.,
5 on barium sulfate, 200 mg., were added and the mixture was stirred at room temperature and under hydrogen (571) mm. pressure) till there was an uptake of 1 mol of hydrogen and the exchange of bromine for hydrogen was The catalyst was removed by filtration and the solvent was evaporated under reduced pressure. crystallization of the residue from acetone hexane gave the acetate of 6B-fiuoro-testosterone, identical with the known compound.
EXAMPLE XXII compounds:
Table IV Starting Material Intermediate Compound Final Compound 17,21-diacetate oi n -pregnendfid'iu,
17-acetate of N-pregnen-SB, 7a-di0l- 20-one.
tSlr-fluoro-cortisone acetate.
6a.94rdifluoro lfia-methylcortisone.
EXAMPLE A solution of l g. of testosterone acetate in cc. of ethyl acetate and in presence of 5 cc. of acetic acid and 2 g. of chloranil was refluxed for 6 hours. the reaction period the mixture was cooled, 25 cc. of ethyl acetate was added, the solution was washed with 5% aqueous sodium hydroxide, water, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure, leaving the acetate of A -androstadien-17-ol-3-one. acetone-hexane gave the pine compound. compound was then treated in accordance with Example I, dissolved in methylene dichloride, with hydrofluoric acid, N-bromoacetamide in presence of tetrahydrofurane and the resulting fifi-fiuoro-i 'a-bromo testosterone acetate isolated by evaporating methylene-chloride and crystallization from ether-heptane.
The above compound, 1 g., dissolved in 100 cc. of ether was treated with 100 mg. of finely divided mag- Crystallization from The above Propionato of 6,8-fluoro-7wbrom0- l7a-hydretry-progesterone. 2l-acctate of fidiluorofiwbromon pregnen-liafil.-dio1-3,20-dione. 21acetvte of fifidiuoroJa-bromo-A pregneudiv Zl-diold,11.20-trioue. 6Q 21-propionatc of ddficz-dilluoro-mbromo-ii -preguen-ll,ide l711,21- tctrol-afiudi-oue 16,17-acctonide. Acetate of pregnen-2i-ol-3,20dione. 21-acetate of it;
4 #pregnadiendifl, 17a, 2ltriol-3,
0 Intermediate Compound Final Compound t 1 17ameth l-6.8tluoro-7a-bromo lie-fluoro-l7wmethyl-testos- At and of testosteione. terone.
6,8-fluUf0 7l-i)TUl11O estrone fifi-fluoro estrone. Acetate of tifi-iluoro-Ta-bromo (SS-fluoro estra-dioi acetate.
estradiol. 1,2-dimethyl-6,6-fluoro-7a-bromo 1,2-dimethyl--fluoro-estrone.
Propionate of 6,6-flu0rod7ahydroxy progesterone. Zl-acetate of 6,8tluoro-A 20-dioue. 65 A M pregnatriend 7a,21-diol-3,20- 66fiuor0-A (l1) -pregnadiendione. 17a,21-di0l-3,20-dione.
nesiurn metal and 5 mg. of iodine (Well mixed, preheated to 150 for 5 minutes, and then cooled in a dessicator) the mixture was stirred first for 5 minutes at room tem- 70 1 perature, was then refluxed for additional 15 minutes, water was then added and the ethereal layer isolated, dried over anhydrous sodium sulfate and evaporated. Crystallization of the residue from acetone-hexane gave the pure acetate of Sfl-fiuoro-testosterone.
EXAMPLE XXIII of the Gfl-fluoro-"la-bromo-testosterone acetate, obtained in accordance with Example XX was dissolved in 25 cc. of dimethyl formamide, 500 mg. of lithium chloride was added and the mixture was refluxed 8 hours under nitrogen atmosphere. period the mixture was filtered, the filtrate was evaporated and palladium pregnen-17a,21-diol-3,20-dione.
At the end of the reaction a venti- I55 under reduced pressure and the residue was crystallized from acetone-hexane to give pure 6-fluor0-A -dehydro testosterone acetate.
EXAMPLE XXIV By the same method as described above but substituting lithium chloride by calcium carbonate, and refluxing only 2 hours, there was produced the acetate of 6-fluoro-A dehydro testosterone in essentially the same yield.
EXAMPLE XXV 1 g. of the 6B-fiuor0-7a-bromo-testosterone acetate, was dissolved in cc. of acetic acid, 1 cc. of concentrated hydrochloric acid was added, and the mixture was refluxed 24 hours. The solution was then cooled, diluted with Water, the precipitate was collected, washed, dried and crystallized from ethyl acetate-ether. The compound thus formed was found to be identical with 6-fluoro-A -dehydro-testosterone acetate, produced as described in Example XXIII.
EXAMPLE XXVI 1 g. of the 65-fiuoro-7'oc-bromo-testosterone acetate, dissolved in 40 cc. of acetic acid, was treated, While stirring and at room temperature, with an aqueous solution of chromous chloride (3 mols); the solution was stirred for minutes, was poured into water'and the precipitate was collected, washed and dried. The compound thus formed was found to be identical with 6,8-fluoro testosterone acetate.
EXAMPLE XXVII By the same method as described above, but substituting 6,8-fluoro-7a-bromo-testosterone acetate by 6fl-fiuoro-7ixbromo progesterone and acetic acid by acetone, there was produced ofi-fluoro progesterone.
EXAMPLE XXVIII By the same method as described in Example XX and XXIV there were prepared theA -dehydro, thte 6fi-fiuoro- 7a-bromo and the 6-fiuoro compounds respectively as indicated in Table V,
Table 1% EXAMPLE XXX By the same method as described in Example XXIII and using the intermediate compounds made in accordance with Example XXI there were prepared 6-fluoro-A -dehydro-estrone, 6-fluoro-A -dehydro estradiol and 1,2- climethyl-o-fiuoro-A -dehydro estrone.
EXAMPLE XXXI wherein X is selected from the group consisting of chlorine, bromine and iodine, X is selected from the group consisting of hydrogen, fluorine, chlorine and bromine, Z is selected from the group consisting of hydrogen, :0 and i R is selected from the group consisting of hydroxyl, keto and ethylenedioxy, R is selected from the group Starting Material Intermediate Compound Final Compound Testosterone undecenoate l7a-ethyl-testosterone noate ilwfluoro-llfi-hydroxy-lia methyl- G 9, 9a-difluoro-7a-bromo-11,811ydroxytestosterone. 17 a-methyl-testosterolie.
Cyclopentyl propionate of 17wmethyl- Cyclopentylpropronate of fifi-fluoro-M- testosterone. bromo-l7a-rnethyltestosteroue.
Progesterone (SB-fluoro-M-bromo-progestorone 17a-acetoxy pr0gester0ne A -pregnen-17a, 21-di0l-3,20-di0ne progesterone.
21-aeetate of A -pregnen-17 a,21-diol- 3,11,20-t1'i0ne.
116, 17a, 21-trio1-3,20-dione. Qa-fluoro-lfia-methyl-hydroeortisone hydrocortisone. ZI-acetate of A -pregnatrien- 17a, 21-diol-3,20-dione.
(id-fluoro-7a-bromotestosterone undece- 21-aeetate of SB-fiuoro-M-bromo-A 1) pregnadien-IM, 2l-diol-3,20-dione.
fi-fluoro-A -dehyrdotestosterone undese- EXAMPLE )QCIX By the same method as described in Example XXIII there were prepared, starting from the fluoro-halo compounds made in accordance with the method described in Example XIII, the corresponding 2-fiuoro-A -dehydro-, -15-fluoro-A -.dehydro-, and lo fluoro-n -dehydro derivatives. More specifically, there were prepared Z-tluoro- 17a-acetoxy-A -dehydro progresterone, 2-fluoro-prednisone, the ZI-acetate of 2,9asditiuoro-prednisolone, 21- acetate of IS-iiuoro A pregnadien-17e,21-diol3,20- dione, 1"6-fluoro A4 pregnadien 3,20 dione and the acetate ,Ojf 1,6flu or o -allopregnen-Zfi-ol-l1,3O--dione.
consisting of hydrogen, hydroxyl and methyl, and R is selected from the group consisting of :0,
/OR15 OOGH3 0043113 oo-onion \RW \H 012 H and oo-crnoa and R is selected from the group consisting of hydrogen and a hydrocarbon carboxylic acyl group of up to 12 17 carbon atoms, and R is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, and lower aikinyl.
2. 5oz bromo-6B-fluoro-17a-methyl-androstan-35,176- diol.
3. The hydrocarbon carboxylic acid esters of up to 12 carbon atoms of 5u-bromo-6B-flu0ro-17u-methyl-androstane-3,B,17,8-diol.
4. 5u-bromo-6;8-fiuoro-pregnan-3,3-01-20-one.
S. Son-bromo-Gfi-fluoro-pregnan-3B,17a-diol-20-one.
6. 5a-bromo-6fi-fluoro-pregnan-17a-ol-3,20-dione.
7. The hydrocarbon carboxylic acid esters of up to 12 carbon atoms of 5u-bromo-6fifluoropregnan-17u-ol- 3,20-dione.
9. 5c: bromo-6p-fluoro-pregnan-17u,21-diol-3,20-dione.
10. 5oz brorno-Gfi-fluoro-M -pregnen-Bfi,16a,170:,21- tetrol-20-one 1 6,17-acetonide.
11. 5a brorno-Gp,9e-difluoro-pregnan-3fl,1113,17a,21- tetroi-ZO-one.
12. 5a bromo-fifi-fluoro-IGu-methyl-pregnan-BB,17a, 21-triol-11,20-dione.
13. The hydrocarbon carboxylic acid esters of up to 12 carbon atoms of 5a-bromo-6fl-fluoro-lfia-methyl-pregnan- 3 3,17oz,21-tlil-11, ZO-dione.
14. e bromo 6B fluoro 16u-methy1-pregnan-16B 17a,21-triol-3,20-dione.
15. 5a bromo-6,6,9e-difiuoro-IGa-methyI-pregnan-Bfi, 11]3,17u,21-tetrol-20-one.
16. 5oz bromo 65,90: difluoro-pregnan-SflJ1,8,16a, 17a,21-pentol-20-one.
17. A process for the fluorination of the double bond between carbon five and six of cyclopentanophenanthrene compounds selected from the class consisting of compounds of the pregnene and androstene series comprising reacting the compound, in the presence of a hydrogen acceptor selected from the group consisting of hydrocarbon ethers and ketones, with hydrofluoric acid and an N-chloro hydrocarbon amide to produce the corresponding 5a chloro-6B-fluoro-cyclopentanophenanthrene compound, there being present in the reaction mixture for each mol of cyclopentanophenanthrene compound, 1 to 100 mols of hydrofluoric acid, 0.1 to 2 mols of hydrogen acceptor, and 0.5 to 1.5 molar equivalents of N-chloro hydrocarbon amide, and the temperature of the reaction mixture is maintained during the reaction below 0 C.
18. A process for the fluorination of the double bond between carbon five and six of cyclopentanophenantbrene compounds selected from the class consisting of compounds of the pregnene and androstene series comprising reacting the compound, in the presence of a hydrogen acceptor selected from the group consisting of hydrocarbon ethers and ketones, with hydrofluoric acid and an N-chloro hydrocarbon imide to produce the corresponding 5a-chloro-6p-fluoro-cyclopentanophenanthrene compound, there being present in the reaction mixture for each mol of cyclopentanophenanthrene compound, 1 to mols of hydrofluoric acid, 0.1 to 2 mols of hydrogen acceptor, and 0.5 to 1.5 molar equivalents of N-chloro hydrocarbon imide, and the temperature of the reaction mixture is maintained during the reaction below 0 C.
19. A process for the fiuorination of the double bond between carbon five and six of cyclopentanophenanthrene compounds selected from the class consisting of compounds of the pregnene and androstene series comprising reacting the compound, in the presence of a hydrogen acceptor selected from the group consisting of hydrocarbon ethers and ketones, with hydrofluoric acid and an N-bromo hydrocarbon amide to produce the corresponding 5a-bromo-6fi-fluoro-cyclopentanophenanthrene compound, there being present in the reaction mixture for each mol of cyclopentanophenanthrene compound, 1 to 100 mols of hydrofluoric acid, 0.1 to 2 mols of hydrogen acceptor, and 0.5 to 1.5 molar equivalents of N-bromo hydrocarbon amide, and the temperature of the reaction mixture is maintained during the reaction below 0 C.
20. A process for the fluorination of the double bond between carbon five and six of cyclopentanophenanthrene compounds selected from the class consisting of compounds of the pregnene and androstene series comprising reacting the compound, in the presence of a hydrogen acceptor selected from the group consisting of hydrocarbon ethers and ketones, with hydrofluoric acid and an N-bromo hydrocarbon imide to produce the corresponding 5a-bromo-6}8-fluoro-cyclopentanophenanthrene compound, there being present in the reaction mixture for each mol of cyclopentanophenanthrene compound, 1 to 100 mols of hydrofluoric acid, 0.1 to 2 mols of hydrogen acceptor, and 0.5 to 1.5 molar equivalents of N-bromo hydrocarbon imide, and the temperature of the reaction mixture is maintained during the reaction below 0 C.
References Cited in the file of this patent UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,173, 914 March 16, 1965 Albert Bowers It is hereby certified that error appears in the above numbered patent reqliring correction and that the said Letters Patent should read as correctedbelow.
In the heading to the printed specification, lines 2 and 3 for "5,6-DIFLUORO STEROIDS AND PROCESS FOR THE PREPARATION THEREOF" read 5- HALO-6-FLUORO STEROIDS AND PROCESS FOR THE PREPARATION THEREOF Signed and sealed this 14th day of September 1965.
(SEAL) lttest:
ERNEST W. SWIDER EDWARD J. BRENNER Hosting Officer Commissioner of Patents
|Cited Patent
|Filing date
|Publication date
|Dec 6, 1951
|Mar 30, 1954
|Thomas Charles L
|Production of fluoro-olefins
|Dec 17, 1952
|Apr 28, 1959
|Merck & Co Inc
|5, 6-dichloro pregnanes
|Citing Patent
|Filing date
|Publication date
|Aug 2, 1965
|Dec 13, 1966
|Roussel Uclaf
|Novel 3-keto-4-fluoro-delta4-steroids and preparation thereof
|Jun 24, 1965
|Feb 14, 1967
|Philips Corp
|Novel 9beta, 10alpha-steroids and process for the manufacture thereof
|Jul 29, 1968
|Nov 17, 1970
|Squibb & Sons Inc
|Acetonides of 9-halogenated 3beta,11beta,10alpha,17alpha,21-pentahydroxypregnanes
|Mar 27, 1970
|Aug 1, 1972
|Schering Ag
|Process for the preparation of 5-bromo-6-fluoro-steroids
|Nov 5, 1979
|May 12, 1981
|Schering Corporation
|Use of 6β-fluoro-7α-halogenocorticoids as topical anti-inflammatories and pharmaceutical formulations useful therefor
|U.S. Classification
|540/69, 552/638, 552/534, 552/635, 552/640, 552/572, 552/538, 552/649, 552/647, 552/597, 552/544, 540/27, 552/603, 552/627, 552/641, 552/598, 552/594, 552/595, 568/714, 552/601, 552/567, 552/628, 552/565, 552/639, 562/403, 568/495, 540/35, 552/550, 552/605, 552/622, 552/573
|International Classification
|Cooperative Classification
|European Classification


text:
Ever since Stefan Pierer bought the Husqvarna brand, we have been curious to see how "Husky" would fit within the KTM family.
As of late, Husqvarna models have been little more than recycled KTM motorcycles, with a few minor changes and some cosmetic tweaks seemingly being the only thing that separates the Swedish brand from its Austrian owner.
Part of this is a necessary evil, as it takes time to design and build new models, with the current overlap at least serving to update the Husqvarna line until actual new models can be released.
In 2017, we will see the first truly new Husqvarna models come to market, the Husqvarna 401 Vitpilen & Husqvarna 401 Svartpilen. Now we can see a third model, which further defines how we will understand Husqvarna in the future, its called the Husqvarna Vitpilen 701 concept.


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Sustainability Saturday: Take 20% off 1+ yards of Eco Canvas Fabric Through 11:59 PM EDT July 30th.
Artist, graphic designer, mom and nature lover based out of Lake Cowichan, Vancouver Island, BC. Loving Spoonflower and connecting with all of you here! Please send me a message if you'd like any colour or scale changes, or just to say hi.
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Broadway star Idina Menzel will headline a Beaches remake for Lifetime. The 1988
Actor and radio host
Big Brother 18 dropped a whole of of twists on us this week. Not only did Victor...
Three different types of trout — Brown, Lake and Rainbow — will be targeted on Saturday as young anglers gather at Rotary Park for the 14th annual Connor Gorsuch Kids' Fishing Day.
MTV is bringing back some of your favorite '90s shows to launch a new network, MTV Classic.
Lake Superior State University Provost David Finley says administrators are working hard to prepare for a November visit from the Higher Learning Commission (HLC).
PHILADELPHIA (AP) Bradley Cooper's appearance at the Democratic National Convention has irked some conservative fans of the actor's portrayal of Navy SEAL Chris Kyle in 2014's "American Sniper."
There was something a little off about the dead whale washed up on St. George Island. It also showed signs of an unusual color, with bits of black skin still clinging to its bloated blubber.
A poll released Thursday showed Hillary Clinton with a massive lead over Donald Trump in Pennsylvania — a state both presidential candidates are zeroing in on.
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The 1999-2005 Harley-Davidson FLH, FLT Twin Cam 88 and 103 repair manual by Clymer covers:
Book Excerpt: 1999-2005 Harley-Davidson FLH, FLT Twin Cam 88 and 103 Repair Manual
Proper suspension and engine alignment is necessary to ensure good motorcycle performance and drivability. The following procedures describe how to check the engine stabilizers and rear axle-to-swing pivot shaft alignment.
Check the following areas for problems caused by normal wear. Adjust, repair or replace components as required.
This chapter covers lubrication, maintenance and tune-up procedures. If a procedure requires more than minor disassembly, reference to the appropriate chapter is listed.
Maintenance intervals, capacities, recommendations and specification are in Tables 1-9 at the end of this chapter.
To maximize the service life of the motorcycle, and gain maximum safety and performance, it is necessary to perform periodic inspections and maintenance.
Minor problems found during routine service can be corrected before they develop into major ones.
Consider the maintenance schedule a guide. Harder than normal use and exposure to mud, water or high humidity indicates the need for more frequent servicing to most maintenance items.
The shipment arrived here in Germany in a few days, everything was O.K and nothing was damaged. This book is a very good stuff: very detailed, highly illustrated with a lot of pictures, tables and figures. It is nearly the same content with a little bit "clearer" form of presentation like the original Harley "Owners Manual" and I think it is a nice add-on for me.
This is the second book I bought at motorbookstore and I'm a satisfied customer!
Lot of greetings from Heusenstamm, Germany (it's near Frankfurt).
~Matthias Weber
This manual contains detailed and easy-to-follow instructions, accompanied by sharp photos and illustrations, guide you through every procedure, from basic maintenance and troubleshooting, all the way to teardown and rebuild.
If you'd like to take care of your own Harley motorcycle, this repair and service manual by Clymer will be a smart addition to your library.
Packed from cover-to-cover with how-to information combined with tons of photos, illustrations, exploded views, charts and diagrams, this DIY guide will come in handy from basic jobs such as scheduled maintenance, all the way to more involved, advanced repairs.
A long-time bestseller here at The Motor Bookstore, the 1999-2005 Harley FLH, FLT Twin Cam 88, 103 repair manual is available at the best price anywhere. Guaranteed!
Wikipedia link: Harley-Davidson FL.
Subject: 1999, 2000, 2001, 2002, 2003, 2004, 2005 Harley-Davidson FLH, FLT Twin Cam 88 and 103 service, maintenance, repair. ISBN-10: 1599690160 ISBN-13: 9781599690162 | Clymer M430-4
TABLE of CONTENTS:
Bob Mitcheltree
5 Stars
I would recommend this item to a friend.
Clymer Book
March 10, 2016
Great book. Very well detailed.
Pros:Has pictures and great explanations on how to fix or repair your bike.
Eddie Jones
Valdosta GA.
4 Stars
I would recommend this item to a friend.
very good technical manual
January 19, 2016
this book is designed for a diy type guy and it will keep you from making stupid mistakes.
Rick Williams Sr
Candler, NC
5 Stars
I would recommend this item to a friend.
More info than OEM shop manual
October 9, 2015
I've been using Clymer for years for my Harley "go to" guide.
Pros:Detailed information and clear illustrations. Wiring diagrams match factory colors.
Cons:Not any I can think of.
Sugarcreek OH
4 Stars
I would recommend this item to a friend.
Overall great
September 4, 2015
Was very reasonably priced an came in mail within a week
Austin, TX
5 Stars
I would recommend this item to a friend.
Good price, prompt shipping.
August 7, 2015
I haven't had the need to use it yet but I know it'll fill the need.
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Pleasant Grove, Calif
4 Stars
I would recommend this item to a friend.
This is a great book
March 31, 2015
Reading and viewing this book is all I expected and more.
4 Stars
I would recommend this item to a friend.
Good, but not complete.
August 12, 2014
Techniques for maintenance and repair are well covered, but a major flaw is the lack of identifying part numbers or description to be able to purchase items required. I guess that is why harley still sells their service manuals


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Baymont Inn and Suites Branson - on The Strip, Branson
- Free continental breakfast, free WiFi, and free parking
Main amenities
- 87 smoke-free guestrooms
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- In Branson Theater District
- Veterans Memorial Museum (0.6 mi / 1 km)
- Dixie Stampede Dinner Attraction (1 mi / 1.6 km)
- Hollywood Wax Museum (2.7 mi / 4.4 km)
- Titanic Museum (2.9 mi / 4.7 km)
- Our Lady of the Lake Catholic Church (0.1 mi / 0.2 km)
For families
- Free cribs/infant beds
- Microwave
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- Connecting/adjoining rooms available
- Private bathroom
- Premium TV channels
Baymont Inn and Suites Branson - on The Strip, Branson
Hotel Info: 020 3027 9803from £84
- Standard Room, 1 Queen Bed, Accessible
- Standard Room, 2 Queen Beds
- Standard Room, 1 Queen Bed
- Standard Room, 1 King Bed
Also popular with travellers from the UK
At a glance
Key facts
Hotel size
- This hotel has 87 rooms
- This hotel is arranged over 5 floors
- Check-in time 3 PM-midnight
- Check-out time is 11 AM
Required at check in
- Credit card or cash deposit required
- Government-issued photo ID required
- Minimum check-in age is 18
Travelling with others
- Pets allowed (dogs only) *
- Restrictions apply *
- 2 per room (up to 75 lb)
- Free WiFi in public areas
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Other information
- Smoke-free property
Nearby Two Star Branson hotels
In the hotel
- Free continental breakfast daily
- Barbeque grills
- Indoor pool
- Fitness facilities
- 24-hour business center
- 24-hour front desk
- Tours/ticket assistance
- Laundry facilities
- Free newspapers in lobby
- Number of buildings/towers - 1
- Elevator/lift
- ATM/banking
- Picnic area
- Accessible bathroom
- In-room accessibility
- Roll-in shower
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- Air conditioning
- Coffee/tea maker
- Iron/ironing board
- Private bathroom
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- 32-inch flat-screen TV
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- Refrigerator
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- In-room safe
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Baymont Inn and Suites Branson - on The Strip, Branson's small print
Also known as
- Baymont Inn Branson Strip Hotel
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- Baymont Inn Strip Hotel
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The property has connecting/adjoining rooms, which are subject to availability and can be requested by contacting the property using the number on the booking confirmation.
Pet-friendly rooms can be requested by contacting the property at the number on the booking confirmation.
Mandatory fees
Pet deposit: USD 25 per stay
Optional extras
Late check-out can be arranged for an extra charge
Safes in guestrooms can be used for USD 1.50 per day
Pets are allowed for an extra charge of USD 40.00 per accommodation, per stay
We have included all charges provided to us by this hotel. However, charges can vary, for example, based on length of stay or the room you book.
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text:
The Polyamorous Test
Their result for The Polyamorous Test ...
You're 72% Poly =) 91% tolerant of the poly lifestyle =) (But... you're 32% just in it for the sex =))
but watch out... you're willing to lie to your mate to protect them, a typical compassionate pot hole - you'd do anything to prevent them from getting hurt right? (And lets face it having them upset at us doesn't help any either...)
Just becareful - some people will lie to protect their loved ones - and end up protecting them from ever knowing who you really are. That's not what you want - you should be finding someone who can love you for who you are and accept all the parts of you with out having to lie about any of them =/ And even that's something you can live with - If you're doing things you can't tell your loved one about anyway... you're not quite as good a person as you think you are =/
Becareful! That's all - end of sermon =)
Much love to you and good luck =)
Gabriel Night
Oh - just so you don't go off wondering - the first question? the one about monogamous cultures? the answer is 16% of recorded cultures have been monogamous - 84% have been non monogamous! how about that? =)
Their Analysis (Vertical line = Average)
They scored 72% on True Poly, higher than 30% of your peers.
They scored 91% on Tolerance, higher than 68% of your peers.
They scored 32% on Sex Only, higher than 91% of your peers.
They scored 38% on Honesty, higher than 91% of your peers.
All possible test results
You're honest, which is a big plus - and you should value that (and obviously do! =)) You didn't come out too high on being polyamorous - but that's ok =) It's not for everyone and even the most ... Read more
You scored a little high on being willing to lie to your mate... this makes me nervous because often the biggest hurts are done with the best intentions - becareful that you're not "protecting" your l... Read more
sex seeker
You're honest, which is a big plus - and you should value that (and obviously do! =)) You didn't come out too high on being polyamorous - but that's ok =) It's not for everyone and even the most ... Read more
Grow UP!
You're not very polyamorous, and you're not very tolerant of poly relationships either... Yet you want to have sex with multiple people and you're willing to lie to your mate about it afterwards. ... Read more
Fave Non Poly =)
You're not very poly yourself (and that's cool - there's nothing wrong with monogamy at all =)) and you're awfully tolerant of poly relationships which is a very cool thing =) On top of that you ... Read more
Non Poly
You're not very poly yourself (and that's cool - there's nothing wrong with monogamy at all =)) and you're awfully tolerant of poly relationships which is a very cool thing too =) (Thanks!) On to... Read more
I'm confused
According to the test you're Not really poly ... But you'd like to have sex with everyone. *But* you wouldn't lie to your mate about it afterwards. (Which is very cool but ... if want to s... Read more
Modern Youth
You didn't score as very polyamorous (which is cool, it's not for everyone and no one wants to force it on anyone =)), but you're tolerant to it in others and that's a cool thing too. However...... Read more
This should be a hard category to get into ... You're poly but intolerant of poly lifestyle... I'm guessing you and I have very different ideas of what it means to be poly ... except of course... Read more
Hmm... You're poly. But intolerant to poly lifestyle. You're not here just for sex, but you're willing to lie to your mate about things that might hurt em... You just confuse the hell o... Read more
Sex Maniac
You're poly... but somewhat intolerant of poly lifestyle... AND you value the sex more than anything. But you're not willing to lie about it to your mate. You're an interesting person. ... Read more
You scored high on being poly... but low on your tolerance of poly people. This admitidly confuses me. In addition to this, you scored high on the "Just want sex sex sex" scale - and high on ... Read more
Heavenly Perfection
Ooooooohhhh Aaaaaaaaahhhhhh You're poly. You're tolerant of poly lifestyle. (Good for you you like yourself!) You're not just here for the sex. And you won't lie to your mate. I ... Read more
A true poly, tolerant and loving, not just here for the sex and all around a good person... but watch out... you're willing to lie to your mate to protect them, a typical compassionate pot hole - ... Read more
Sexy Poly
You're a true poly, but you _love_ the sex - remember to value the love itself and the astounding rarity of the relationship you've been lucky enough to find - at least you're honest with the people y... Read more
Pride before da fall
You sex loving compassionate arrogant polyamorous wild one you! You're a good person, with a lot of love in your heart - but watch out - sex can easily trip you up - and your willingness to lie ab... Read more
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text: Item is not available Find Another One Others Looked At... Ruger .44 Special Flattop - Consecutiv... SELLER: GGray 0 $1,075.00 LNIB 1978 Ruger New Model BlackHawk .357... SELLER: Ammo And Arms 1 $499.99 1976 Bicentennial Ruger BlackHawk Conver... SELLER: Ammo And Arms 1 $1,499.99 RUGER 50TH ANN. FLAT TOP .44 MAG CUSTOM.... SELLER: latigo 0 $785.00 Ruger Blackhawk .357 mag SELLER: SHORE SPORTSMAN 1 $650.00 Ruger Blackhawk Flat Top 3-Screw SELLER: Deerhunter39 0 $1,495.00 Guns Pistols Ruger Single Action Revolvers Blackhawk Type RUGER NEW MODEL BISLEY BLACKHAWK RB W COLT SINGLE ACTION REVOLVER W . BARREL | 583 | 58 | Lc | 359.2818ms RUGER NEW MODEL BISLEY BLACKHAWK (RB-45W) 45 COLT SINGLE ACTION REVOLVER W/ 7.5" BARREL (00447) For Sale from Bizarre Guns | Positive feedback: 100% View | Verified Seller | 819 Completed Sales View Sellers Items This item is no longer available. /UserImages/124428/986040624 3872917.jpg /UserImages/124428/986040624 3872918.jpg /UserImages/124428/986040624 3872919.jpg /UserImages/124428/986040624 3872920.jpg Description Shipping and Payment More Info New in box. New Model Blackhawk 45LC single action revolver with Bisley grips and hammer, 7.5" barrel, adjustable sights, and engraved cylinder. Prices listed reflect a cash discount. We treat Visa and Mastercard same as cash. Please add 3% to the total price for Discover or American Express. Ask about our instore layaway terms. We are only available by phone Monday thru Friday, 10:00AM to 5:00PM Pacific. Please note that even if you click the buy button, you will still need to contact us to receive instructions on how to pay for and have your firearm shipped to a nearby FFL dealer. We will only ship to FFL dealers, and only after an exchange of FFL's. Please make sure this firearm is legal to own in your state or municipality before committing to buy. We reserve the right to refuse any and all sales of firearms at our discretion. All listed items are subject to prior sale from our bricks and mortar business. All sales are final. All warranty services on new firearms must be done solely through the manufacturer. All used firearms are sold as is. We charge $30.00 USPS Priority Mail shipping, insurance included on this item. We will only ship firearms to FFL dealers. Please inquire regarding other shipping options. Trades Accepted: We will not make trades. Condition: New In Box Caliber: .45 Colt Location: NV Share Item Item #: 986040624 Stock No.: 21414 This item is no longer available. Price: Shipping: $30.00 (or Arrange local transfer) Accepted Payment Methods: Returns: No Returns Bizarre Guns Seller Since: Oct. 2010 Seller Level: Gold Seller + This seller is an FFL City: Reno State: NV More Items from this Seller ( 86 items total | View All ) CENTURY ARMS GRAND POWER ... $509.00 Full Details Add To Cart Henry Big Boy Mares Leg .... $819.00 Full Details Add To Cart KIMBER GOLD MATCH II 45AC... $1,179.00 Full Details Add To Cart Mc | 31.2526ms -- 124428 Your Recently Viewed Items


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It is shown that if a nonlinear system is linearly controllable, then it can always lead to the linearization condition through state feedback, provided the transformation satisfies an additional condition on the system input. The methodology proposed is to make the eigenvalues of the Jacobian of the system nonresonant. The generality of the proposed method allows the eigenvalues of the linear system to be arbitrarily placed inside a scalable circular region in the left half of the complex plane. The method is illustrated with an example
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Rushpool Hall in Saltburn-by-the-Sea, North Yorks, a Victorian spa resort, was built originally as a Country Manor house and was described by Victorians as being "one of the most picturesque Country Mansions in North Yorkshire."
Without doubt it is still an outstanding example of Victorian architecture not to be missed. Rushpool Hall has for many years operated as a Weddings & Private Functions Venue, it is, in a nutshell, the "Dream Location" for every type of Celebration
Well spotted Ian and there's me thinking you wouldn't see it parked near the door Cheers
A big LIKE for this shot and the two before of this stunning looking country manor house. I can imagine that the owner of the red Ferarri in front also will be the owner of this impressive building and garden.
I Would Imagine To Jack Many Thanks
A lovely capture Richard, reading the blurb up top I'm guessing that's from their advertising, if not you ought to be on commission :o)
Thanks Sam and yes it's there advertising, my oldest daughter spent her wedding night there
Wonderful Victorian structure Richard, nicely captured. Lk it. Regards, Jock.
Thanks Jock it's a lovely place
Photo taken in Skelton and Brotton, Redcar and Cleveland, UK
Rushpool Hall Hotel


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Sächsisches Eisenbahnmuseum in Chemnitz Hilbersdorf
El Retaule de Guimerà va ser pintat per Ramon de Mur, és una de les obres pictòriques més importants del gòtic català. Va ésser pintat entre 1402 i 1412 aproximadament, segons les breus referències de recollida d'almoines per pagar el retaule. És un retaule grandiós, dels més grans de l'època, amb unes mide...
See in 3D virtual reality: loughridge.com/Lyon02 . This aircraft is on display at the Lyon Air Museum in Orange Couny, CA.
See in 3D Virtual reality: loughridge.com/Lyon03 . This aircraft is also known as the B26 Invader. . Douglas Aircraft Company built 2,448 of these (all models). It had a top speed of 355 MPH. It had a crew of three... the pilot, bombardier and gunner. This aircraft has two Pratt and Whitney 2,000 horsepower...
This motorcycle is on display in the Lyon Air Museum in Orange County, CA at the John Wayne Airport. See in 3D Virtual Reality: loughridge.com/motorcycle
The Lyon Air Museum is in Orange County, California. It displays World War II vintage bombers and motorcycles. See in 3D: loughridge.com/Lyon01
This image is intended to give the viewer a sense of what they would have experienced had they been able to visit the da Vinci exhibit at the Muscarelle Museum of Art at the College of William & Mary in Williamsburg, Va between February and April, 2015. This panoramic image measures nearly 22' long and consists of 3...


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Glendale arena hosting job fair
PHOENIX — A popular arena in Glendale, Ariz., is hiring for the fall.
The Jobing.com Arena will host a job fair on July 17. They will be hiring "part-time workers to staff upcoming events at the arena, including for next season's Arizona Coyotes game," the Phoenix Business Journal reported.
Jobs available include housekeepers, security, ushers, guest services and parking lot attendants.
The free job fair will run from 4 to 8 p.m. The arena is located at 5400 W. Maryland Ave.
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