<!--

       Copyright 2011 Peter Murray-Rust et. al.

       Licensed under the Apache License, Version 2.0 (the "License");
       you may not use this file except in compliance with the License.
       You may obtain a copy of the License at

           http://www.apache.org/licenses/LICENSE-2.0

       Unless required by applicable law or agreed to in writing, software
       distributed under the License is distributed on an "AS IS" BASIS,
       WITHOUT WARRANTIES OR CONDITIONS OF ANY KIND, either express or implied.
       See the License for the specific language governing permissions and
       limitations under the License.

-->

<cml xmlns="http://www.xml-cml.org/schema">
<moleculeList>
  <molecule id="m1" title="2-phenyl....">
    <formula concise="C 17 H 27 N 1 O 2"/>
  </molecule>
  <molecule id="m2" title="triethylamine">
    <formula concise="C 6 H 15 N 1"/>
  </molecule>
  <molecule id="m3" title="2-bromopropanoyl bromide">
    <formula concise="C 3 H 4 Br 2 O 1"/>
  </molecule>
</moleculeList>

<reactionScheme title="Synthesis of Asymmetric initiators" id="ex2">
  <reaction title="Synthesis of 2a">
    <object id="o1" type="apparatus">Round Bottom Flask</object>
    <reactantList>
      <reactant id="r1" count="1" title="2-phenyl-2-1-ethanol">
        <molecule ref="m1"/>
        <amount id="a1" units="units:g">0.85</amount>
        <amount id="a1m" units="units:mmol">3.06</amount>
      </reactant>
      <reactant id="r2" count="1" title="ET3N">
        <molecule ref="m2"/>
        <amount id="a2" units="units:g">0.7</amount>
        <amount id="a2m" units="units:mmol">5</amount>
      </reactant>
      <reactant id="r3" count="1" title="2-bromo propanyol bromide">
        <molecule ref="m3"/>
        <amount id="a3" units="units:ml">0.53</amount>
        <amount id="a3m" units="units:mmol">5</amount>
      </reactant>
    </reactantList>
    <substanceList>
      <substance id="ss1" count="2" role="subst:Solvent">
        <molecule id="m4" ref="THF2"/>
        <amount id="a4" units="units:ml">20</amount>
      </substance>
    </substanceList>
    <conditionList>
      <scalar id="sc1" dictRef="cml:method">stirred</scalar>
      <scalar id="sc2" dictRef="cml:temp" units="units:celsius">0</scalar>
      <scalar id="sc3" dictRef="cml:atmosphere">nitrogen</scalar>
      <scalar id="sc4" dictRef="cml:time" units="units:hour">1</scalar>
      <scalar id="sc5" dictRef="cml:temp" units="units:celsius">21</scalar>
      <scalar id="sc6" dictRef="cml:time">overnight</scalar>
    </conditionList>
    <productList>
      <product id="p1" count="1" title="2a" color="pale yellow" state="oil">
        <molecule id="m9" ref="2-phenyl-2-ethyl 2 bromo-propanate"/>
        <amount id="a5" units="units:gram">0.52</amount>
        <amount id="a6" units="units:percent">41</amount>
      </product>
    </productList>
    <actionList>
    
      <substanceList role="workup">
        <substance id="ss2" role="subst:Solvent">
        <molecule id="m5" ref="CH2CL2"/>
      </substance>
      <substance id="ss3" role="subst:Solvent">
        <molecule id="m6" ref="NA2CO3"/>
      </substance>
      <substance id="ss4" role="subst:Solvent">
        <molecule id="m7" ref="NA2SO4"/>
      </substance>
      <substance id="ss5" role="subst:Solvent">
        <molecule id="m8" ref="hexane"/>
        <amount id="a5" unitType="unitType:vol">8</amount>
      </substance>
      <substance id="ss6" role="subst:Solvent">
        <molecule id="m9" ref="ethyl"/>
        <amount id="a6" unitType="unitType:vol">2</amount>
      </substance>
      </substanceList>
      
      <action title="Step1">
        <reactant>r1</reactant>
        <reactant>r2</reactant>
        <condition>sc1</condition>
        <condition>sc2</condition>
        <condition>sc3</condition>
      </action> 
      <action title="Step2">
      <reactant>r3</reactant>
    <substance>ss1</substance>
    <condition>sc4</condition>
    </action>
    <action title="Step3">
    <condition>sc1</condition>
    <condition>sc5</condition>
    <condition>sc6</condition>
    </action>
    <action title="Step4">
    <substance>ss2</substance>
    <substance>ss3</substance>
    <substance>ss4</substance>
    </action>
    <action title="Step5-Purification">
    <substance>ss5</substance>
    <substance>ss6</substance>
    </action>
    </actionList>
    </reaction>
    
    <reaction title="Synthesis of 2b">
    <object id="o1" type="apparatus">Round Bottom Flask</object>
    <reactantList>
    <reactant id="r1" count="1" title="2-phenyl-2-1-ethanol">
    <molecule id="m1" ref="2-phenyl-2-1-ethanol"/>
    <amount id="a1" units="units:g">0.85</amount>
    </reactant>
    <reactant id="r2" count="1" title="ET3N">
    <molecule id="m2" ref="ET3N"/>
    <amount id="a2" units="units:g">0.7</amount>
    </reactant>
    <reactant id="r3" count="1" title="2-bromo propanyol bromide"
    added="dropwise">
    <molecule id="m3" ref="2-bromo propanyol bromide"/>
    <amount id="a3" units="units:ml">0.53</amount>
    </reactant>
    </reactantList>
    <substanceList>
    <substance id="ss1" role="subst:Solvent">
    <molecule id="m4" ref="DRY THF"/>
    <amount id="a4" units="units:ml">40</amount>
    </substance>
    <substance id="ss2" role="subst:Solvent">
    <molecule id="m5" ref="CH2CL2"/>
    </substance>
    <substance id="ss3" role="subst:Solvent">
    <molecule id="m6" ref="NA2CO3"/>
    </substance>
    <substance id="ss4" role="subst:Solvent">
    <molecule id="m7" ref="NA2SO4"/>
    </substance>
    <substance id="ss5" role="subst:Solvent">
    <molecule id="m8" ref="hexane"/>
    <amount id="a7" units="vol">9</amount>
    </substance>
    <substance id="ss6" role="subst:Solvent">
    <molecule id="m9" ref="ethyl"/>
    <amount id="a8" units="vol">1</amount>
    </substance>
    </substanceList>
    <conditionList>
    <scalar id="sc1" dictRef="cml:methord">stirred</scalar>
    <scalar id="sc2" dictRef="cml:temp" units="units:celsius">0</scalar>
    <scalar id="sc3" dictRef="cml:atmosphere">nitrogen</scalar>
    <scalar id="sc4" dictRef="cml:time" units="units:hour">1</scalar>
    <scalar id="sc5" dictRef="cml:temp" units="units:celsius">21</scalar>
    <scalar id="sc6" dictRef="cml:time">overnight</scalar>
    </conditionList>
    <productList>
    <product id="p1" count="1" title="2b" color="pale yellow" state="oil">
    <molecule id="m9" ref="2-phenyl-2-ethyl 2 bromo-methyl-propanate"/>
    <amount id="a9" units="units:gram">0.52</amount>
    <amount id="a10" units="units:percent">41</amount>
    </product>
    </productList>
    <actionList>
    <action title="Step1">
    <reactant>r1</reactant>
    <reactant>r2</reactant>
    <condition>sc1</condition>
    <condition>sc2</condition>
    <condition>sc3</condition>
    </action>
    <action title="Step2">
    <reactant>r3</reactant>
    <substance>ss1</substance>
    <condition>sc4</condition>
    </action>
    <action title="Step3">
    <condition>sc1</condition>
    <condition>sc5</condition>
    <condition>sc6</condition>
    </action>
    <action title="Step4">
    <substance>ss2</substance>
    <substance>ss3</substance>
    <substance>ss4</substance>
    </action>
    <action title="Step5-Purification">
    <substance>ss5</substance>
    <substance>ss6</substance>
    </action>
    </actionList>
    </reaction>
    <reaction title="Synthesis of macroinitiators - General">
    <object id="o2" type="apparatus">
    Shlenk Tube equiped with magnetic stirring bar ligand
    </object>
    <object id="o3" type="apparatus">Column of Neutral Alumina</object>
    <reactantList>
    <reactant id="r4" count="1" title="catalyst">
    </reactant>
    <reactant id="r5" count="1" title="degassed monomer">
    </reactant>
    <reactant id="r7" count="1" title="initiator">
    </reactant>
    </reactantList>
    <substanceList>
    <substance id="ss6" role="subst:Solvent">
    </substance>
    <substance id="ss4" role="subst:Solvent">
    <molecule id="m4" ref="DRY THF"/>
    <amount id="a4" units="units:ml">40</amount>
    </substance>
    <substance id="ss7" role="subst:Solvent">
    <molecule id="m9" ref="Methanol"/>
    </substance>
    </substanceList>
    <conditionList>
    <scalar id="sc7" dictRef="cml:cycle">three freeze pump cycles</scalar>
    <scalar id="sc8" dictRef="cml:atmosphere">vacuum</scalar>
    <scalar id="sc9" dictRef="cml:temp" units="units:celsius">given</scalar>
    <scalar id="sc10" dictRef="cml:temp" units="units:celsius">50</scalar>
    <scalar id="sc11" dictRef="cml:atmosphere">pressure</scalar>
    </conditionList>
    </reaction>
    <reaction title="Synthesis of macroinitiators - PMMA">
    <object id="o2" type="apparatus">
    Shlenk Tube equiped with magnetic stirring bar ligand
    </object>
    <object id="o3" type="apparatus">Column of Neutral Alumina</object>
    <reactantList>
    <reactant id="r4" count="1" title="PMDETA">
    </reactant>
    <reactant id="r5" count="1" title="degassed monomer">
    </reactant>
    <reactant id="r7" count="1" title="2b">
    
    </reactant>
    </reactantList>
    <substanceList>
    <substance id="ss6" role="subst:Solvent">
    <molecule id="m8" ref="DPE"/>
    <amount id="a6" units="units:ml">50</amount>
    </substance>
    <substance id="ss4" role="subst:Drying Agent-Solvent">
    <molecule id="m4" ref="DRY THF"/>
    <amount id="a4" units="units:ml">40</amount>
    </substance>
    <substance id="ss7" role="subst:Solvent">
    <molecule id="m9" ref="Methanol"/>
    </substance>
    </substanceList>
    <conditionList>
    <scalar id="sc7" dictRef="cml:cycle">three freeze pump cycles</scalar>
    <scalar id="sc8" dictRef="cml:atmosphere">vacuum</scalar>
    <scalar id="sc9" dictRef="cml:temp" units="units:celsius">90</scalar>
    <scalar id="sc10" dictRef="cml:temp" units="units:celsius">50</scalar>
    <scalar id="sc11" dictRef="cml:atmosphere">pressure</scalar>
    </conditionList>
    </reaction>
    <reaction title="Synthesis of macroinitiators - PtBA">
    <object id="o2">
    Shlenk Tube equiped with magnetic stirring bar ligand
    </object>
    <object id="o3">Column of Neutral Alumina</object>
    <reactantList>
    <reactant id="r4" count="1" title="CuBr/PMDETA">
    </reactant>
    <reactant id="r5" count="1" title="degassed monomer">
    </reactant>
    <reactant id="r7" count="1" title="2a">
    
    </reactant>
    </reactantList>
    <substanceList>
    <substance id="ss6" role="subst:Solvent">
    <molecule id="m8" ref="DPE"/>
    <amount id="a6" units="units:ml">50</amount>
    </substance>
    <substance id="ss4" role="subst:Solvent">
    <molecule id="m4" ref="DRY THF"/>
    <amount id="a4" units="units:ml">40</amount>
    </substance>
    <substance id="ss7" role="subst:Solvent">
    <molecule id="m9" ref="Methanol"/>
    </substance>
    </substanceList>
    <conditionList>
    <scalar id="sc7" dictRef="cml:cycle">three freeze pump cycles</scalar>
    <scalar id="sc8" dictRef="cml:atmosphere">vacuum</scalar>
    <scalar id="sc9" dictRef="cml:temp" units="units:celsius">90</scalar>
    <scalar id="sc10" dictRef="cml:temp" units="units:celsius">50</scalar>
    <scalar id="sc11" dictRef="cml:atmosphere">pressure</scalar>
    </conditionList>
  </reaction>
</reactionScheme>
</cml>
