It has median survival rate ranging from 12 to 14 months from the time Our aim in the creation of a model system is to allow sufficient. and select About Tableau Server. For Tableau Bridge, use the same drivers as Tableau Desktop. Data Source. Licensing & Activation: Installation & Deinstallation Are Maintenance Updates Free? Industry Relations: Artist & Content Creator Requests.
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Transition-metal-free intramolecular Friedel–Crafts reaction by alkene activation: A method for the synthesis of some novel xanthene derivatives
Our starting alkenes 4a–l are original and were synthesized in four steps involving coupling, Grignard, oxidation, and Wittig reactions. We synthesized the novel unactivated alkenes 4a–l containing three aryl groups as the starting materials. The synthesis of 4a is demonstrated in Scheme 1. First, 2-phenoxybenzaldehyde (1a) was synthesized by coupling reaction of phenol with commercial 2-fluorobenzaldehyde. This reaction was carried out with very high yield by refluxing the reactants in the presence of K2CO3 in DMF.
2-Phenoxybenzaldehyde (1a) was converted into secondary alcohol derivative 2a by adding a phenyl group using a Grignard reaction. This reaction was carried out with high yield by adding the freshly prepared Grignard compound of phenyl bromide to 2-phenoxybenzaldehyde. As a result, phenoxy secondary alcohol 2a containing three aromatic rings was obtained. In the third step, 2a was oxidized and the ketone derivative 3a was obtained in high yield. The oxidation reaction was carried out using PCC in DCM at room temperature. In the fourth and final step, phenoxydiphenylalkene derivative 4a was prepared by a Wittig reaction, which was carried out using methyltriphenylphosphonium bromide with ketone 3a, in basic medium, at room temperature, and dry THF.
After the structures of the starting compounds were elucidated, the method development trials for the synthesis of xanthene derivatives were carried out. For this purpose, catalyst researches were carried out using compound 4a. An intramolecular Friedel–Crafts reaction was tried by activating the alkene with various organic Brønsted acids and Lewis acids (Table 1). In the reaction, iron(III) chloride hexahydrate, trifluoroacetic acid (TFA), N-trifylphosphoramide (NTPA), benzoic acid, diphenyl phosphate (DPP), malonic acid, chloroacetic acid, copper(II) triflate, acetic acid, and p-toluenesulfonic acid (p-TSA) were used as catalysts. TFA gave the best yield of these catalysts with 78% (Table 1, entry 2). The second-best yield was 65% when FeCl3·6H2O was used (Table 1, entry 1).
|Entry||Catalyst (10 mol %)||Conv. (%)b|
aConditions: 4a (0.1 mmol) and catalyst (10 mol %) in CHCl3 (1 mL) were stirred at room temperature for 24 hours. bConversions were determined with GC–MS.
Then the solvent was investigated. Toluene, methyl alcohol, ethyl acetate, THF, DMF, dichloromethane, chloroform, acetone, and acetonitrile were tested as solvents. As a result, it was determined that the best conversion was with dichloromethane (Table 2). Later, quantity and time experiments were performed (Table 2, entries 10–15) and, at the end of these trials, it was determined that the reaction was completed with >99% conversion in 6 hours with 10 mol % catalyst at room temperature (Table 2, entry 14).
|Entry||Cat. amount (mol %)||Solvent||Time||Conv.b|
aConditions: 4a (0.1 mmol) and TFA in dry solvent (1 mL) were stirred at room temperature. bConversions were determined with GC–MS.
After determining the most suitable conditions for the intramolecular Friedel–Crafts reaction with alkene activation, the synthesis of the new xanthene derivatives was performed according to this method. The synthesized xanthene derivatives with their isolated yields are shown in Figure 1. Compounds 5b–l were synthesized for the first time in this study. The first synthesis of 5a was prepared by reduction of the corresponding xanthydrol  and was also synthesized recently by a different method from our group .
Although in the reactions for FCA reagents and strong inorganic acids, such as AlCl3, H2SO4, or H3PO4, which have generally corrosive properties, were used, in this study, an intramolecular ring closure reaction was carried out under easy operating conditions with an organic Brønsted acid catalyst with high yields. So, the xanthene synthesis with alkene activation was performed for the first time using TFA. The reasonable mechanism of this reaction is delineated in Scheme 2.
Despite this reaction occurring by the classical Friedel–Crafts mechanism, we believe that o-quinone methide is formed as an intermediate. Because of its very reactive structure, most of the xanthene synthesis is based on the o-quinone methide intermediate [54-58]. The carbocation formed by the activation of an alkene with acid turns into an intermediate o-quinone methide, resulting in a successful cyclization.
As seen in the mechanism, the acid catalyst adds to the vinyl group, allowing the formation of a tertiary carbocation. The carbocation is then transformed into the o-quinone methide intermediate, which undergoes cyclization to yield 9-methyl-9-arylxanthene by aromatization. When the yields of the synthesized compounds are examined, it is seen that the yields are high when there is no substituent at the ring to which the carbocation is attached or when there is an electron-donating group, such as a methoxy or methyl group (Figure 1). When there are electron-withdrawing groups, such as chlorine or cyano groups, in the ring, the yield is slightly reduced because they deactivate the ring in the transition state. The lowest yield was observed for compound 5j to which a cyclopentyl group is attached. Since the cyclopentyl group in this compound is directly attached to the carbon from which the carbocation is formed, byproducts are formed and the yield is reduced since conversions can occur.
Types of talking therapy
Talking therapies are psychological treatments for mental and emotional problems like stress, anxiety and depression.
There are lots of different types of talking therapy, but they all involve working with a trained therapist.
This may be one-to-one, in a group, online, over the phone, with your family, or with your partner.
The therapist helps you find answers to the problems you're having.
For some problems and conditions, one type of talking therapy may be better than another.
Different talking therapies also suit different people.
Talking therapies on the NHS
You can get talking therapies like counselling for depression and cognitive behavioural therapy (CBT) on the NHS.
You can refer yourself directly to an NHS psychological therapies service (IAPT) without a referral from a GP.
Find an NHS psychological therapies service (IAPT)
If you prefer, see a GP and they can refer you and share relevant information about you.
Psychological therapies services are also known as Improving Access to Psychological Therapies (IAPT) services.
Cognitive behavioural therapy (CBT)
The aim of CBT is to help you explore and change how you think about your life, and free yourself from unhelpful patterns of behaviour.
You set goals with your therapist and may carry out tasks between sessions.
A course usually involves around 12 to 20 sessions.
CBT has been shown to work for a variety of mental health problems, including:
CBT is available on the NHS for people with depression, anxiety disorders and other mental health problems that it's been proven to help.
Read more about talking therapies on the NHS.
There are also self-help books and computer courses based on CBT to help you overcome common problems like depression.
Find out more about CBT
Guided self-help is recommended as a treatment for depression, anxiety and panic disorder.
With guided self-help you work through a CBT-based workbook or computer course with the support of a therapist.
The therapist works with you to understand your problems and make positive changes in your life.
Guided self-help aims to give you helpful tools and techniques that you can carry on using after the course has finished.
During the course your therapist will support you with face-to-face appointments or phone calls.
See some more self-help therapies.
Counselling is a talking therapy where you talk in confidence to a counsellor. They help you find ways to deal with difficulties in your life.
You may be offered counselling on the NHS if, for example, you:
- are struggling to cope with a long-term condition
- have chronic pain
- have an addiction
- are having fertility problems
Counselling on the NHS usually consists of 6 to 12 sessions.
Read more about counselling.
Counselling for depression
Counselling for depression has been specially developed to help people understand the underlying causes of their depression.
Counselling for depression is available through psychological therapies services.
It's usually offered to people who have mild to moderate depression and have already tried other therapies, such as guided self-help.
Behavioural activation is a talking therapy that aims to help people with depression take simple, practical steps towards enjoying life again.
It may be offered one-to-one or in a group with regular meetings or phone calls with a therapist.
The aim is to give you the motivation to make small, positive changes in your life.
You'll also learn problem-solving skills to help you tackle problems that are affecting your mood.
You'll usually be offered about 16 to 20 sessions.
Interpersonal therapy (IPT)
IPT is a talking treatment that helps people with depression identify and address problems in their relationships with family, partners and friends.
The idea is that poor relationships with people in your life can leave you feeling depressed.
Depression can in turn make your relationships with other people worse.
You may be offered IPT if you have severe depression or depression that hasn't responded to other talking therapies, such as CBT.
IPT is usually offered over 16 to 20 sessions.
Eye movement desensitisation and reprocessing (EMDR)
EMDR is another talking therapy that's been developed to help people who have post-traumatic stress disorder (PTSD).
People who have PTSD may experience intrusive thoughts, memories, nightmares or flashbacks of traumatic events in their past.
EMDR helps the brain reprocess memories of the traumatic event so you can let go of them.
EMDR can be a distressing process, so it's important to have a good support network of family and friends around you if you plan to try it.
A course of treatment is likely to be 8 to 12 sessions.
Mindfulness-based cognitive therapy (MBCT)
Mindfulness-based therapies help you focus on your thoughts and feelings as they happen moment by moment.
They can be used to help treat depression and addiction.
Mindfulness-based cognitive therapy (MBCT) combines mindfulness techniques like meditation and breathing exercises with cognitive therapy.
MBCT is one of the options that may be offered to you after a course of treatment for depression to help stop it coming back.
Read more about mindfulness.
You can find mental health apps and tools in the NHS apps library.
Video: Psychological therapies for stress, anxiety and depression
Animated video explaining self-referral to psychological therapies services for stress, anxiety or depression.
Media last reviewed: 1 September 2021
Media review due: 1 September 2024
Online license activation
Offline (manual) license activation
To use Unity, you need an activated licence. For Unity Plus and Pro licenses, you need to get a serial number; for a Unity Personal license, you don’t need a serial number. To see what kinds of licences Unity offers, go to the Unity Store.
Tip: You should always sign into the Unity ID dashboard in order to access anything you purchased from the Asset StoreA growing library of free and commercial assets created by Unity and members of the community. Offers a wide variety of assets, from textures, models and animations to whole project examples, tutorials and Editor extensions. More info
See in Glossary, or any licenses your Organization granted you. If you don’t have a Unity ID yet, open the Unity ID dashboard to create one.
To activate a Unity Personal license, you must go to the Unity Hub and answer some questions about your situation and for what purposes you plan to use Unity. For more information, see Activating a licence in the Hub.
To activate a Unity Plus or Pro license, you need to provide the serial number for the machine you want to activate it on. For single licenses, Unity emails the license information and serial number to the purchaser.
If you don’t know your Unity license information, speak to the Owner of your license. Owners can assign a seat to you via the Organization, or you can contact Unity Customer Service.
You can activate your license either through the Unity Hub or the command line:
Activating a licence in the Hub
If you haven’t installed the Hub yet, you can download it from the Download Unity web page. Then follow these steps:
Select the Settings button from the top right of the Hub. The Preferences window appears.
Select License Management from the list on the left.
If you see a message at the bottom of the window warning you that you need to be logged in to manage your license, select the LOGIN button from the bottom right and then enter your Unity ID and password.
Important: You can’t activate your license in the Unity Hub unless you are signed into your Unity ID.
Select the ACTIVATE NEW LICENSE button. The New License Activation window appears.
Select which license type you are activating:
- If you select the Unity Personal option, you must select either of the options which best describes your current situation and click Done.
- If you select the Unity Plus or Pro option, enter the Serial Number you received in an email when you purchased a single license. You need to enter the key in the exact format that it appears in the email. For example, .
Note: To activate an educational license select the Unity Plus or Pro option.
Click DONE. Unity displays a success message.
If Unity displays an error message that the license activation was not successful, check Activation issues to find a solution for your issue.
Activating a license from the command line
Before activating your Unity license on the command line, make sure that the license file folder exists and you have write permission.
Note: The command line procedure only works for Plus and Pro licenses because Personal licenses do not have serial numbers associated with them. Use the Unity Hub to activate Personal licenses.
On macOS, enter the following into the Terminal to launch Unity and activate your license:
Replace with the actual path to your Editor installer. Typically, this is usually something like on macOS.
Tip: If you use continuous integration (CI) tools like Jenkins to activate via the command line, add the flag to prevent a WindowServer error.
On Windows, enter the following into the Command Prompt to launch Unity and activate your license:
Replace with the actual path to your Editor installer. Typically, this is usually something like on Windows.
Wait a few seconds after running this command to give Unity enough time to communicate with the license server. If activation fails, you can open the Editor.log for information. For any activation errors, check Activation issues to find a solution for your issue.
Offline (manual) license activation
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