2-(Acetoacetoxy)ethyl methacrylate → 1-Methylcyclopentyl methacrylate

HRID 1910374Notes

Reaction equation

HRID 1910374 reaction equation
[C:1]([O:6][CH2:7][CH2:8][O:9][C:10](=[O:15])[CH2:11][C:12]([CH3:14])=[O:13])(=[O:5])[C:2]([CH3:4])=[CH2:3].[C:16]([O:21][CH:22]1[CH:29]2[CH2:30][CH:25]3[CH2:26]C(C[C:23]1(C(C)C)C3)C2)(=[O:20])[C:17]([CH3:19])=[CH2:18].C(OC1(C)CCCC1)(=O)C(C)=C.C(OC1CCOC1=O)(=O)C(C)=C.[C:59]([O:64][CH:65]1[CH2:73][CH:72]2[O:74][CH:66]1[CH:67]1[CH:71]2[C:70](=[O:75])[O:69][CH2:68]1)(=[O:63])[C:60]([CH3:62])=[CH2:61]>O1CCCC1>[C:16]([O:21][C:22]1([CH3:23])[CH2:29][CH2:30][CH2:25][CH2:26]1)(=[O:20])[C:17]([CH3:19])=[CH2:18].[C:59]([O:64][CH:65]1[CH2:73][CH:72]2[O:74][CH:66]1[CH:67]1[CH:71]2[C:70](=[O:75])[O:69][CH2:68]1)(=[O:63])[C:60]([CH3:62])=[CH2:61].[C:1]([O:6][CH2:7][CH2:8][O:9][C:10](=[O:15])[CH2:11][C:12]([CH3:14])=[O:13])(=[O:5])[C:2]([CH3:4])=[CH2:3]

Participants

8

Reactant 5

HCID 888552-(Acetoacetoxy)ethyl methacrylate2×HCID 11206014gamma-Butyrolactone methacrylateHCID 155392071-Methylcyclopentyl methacrylateHCID 221688401-Oxooctahydro-4,7-epoxyisobenzofuran-5-yl methacrylateHCID 668625631-Isopropyl-adamantanyl methacrylate

Product 2

HCID 155392071-Methylcyclopentyl methacrylateHCID 131731069HCID 131731069, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

An exemplary AAEM-based photoresist polymer (Polymer 1) was prepared according to a procedure similar to the following procedure. A solution of 1-isopropyl-adamantanyl methacrylate (IPAMA) (20 mmol), 1-methylcyclopentyl methacrylate (MCPMA) (20 mmol), 2-oxo-tetrahydro-furan-3-yl methacrylate (α-GBLMA) (30 mmol), 3-oxo-4,10-dioxa-tricyclo[5.2.1.02,6]dec-8-yl methacrylate (ODOTMA) (20 mmol), and 2-(acetoacetyloxy)ethyl methacrylate (AAEM) (10 mmol) dissolved in 30 g of tetrahydrofuran (THF) is degassed by bubbling with nitrogen and charged to a 500 ml flask equipped with a condenser, nitrogen inlet and mechanical stirrer, along with an additional 10 g of degassed THF. The solution is brought to reflux, and 5 g of dimethyl-2,2-azodiisobutyrate is dissolved in 5 g of THF and charged in to the flask. The polymerization mixture is then stirred for about 4 hours at reflux, after which time the reaction is diluted with 5 g of THF and the polymerization mixture cooled to room temperature. The polymer is precipitated by addition to 1.0 L of isopropanol, collected by filtration, re-precipitated by dissolving in 50 g THF and addition to another 1.0 L isopropanol, and collected and dried under vacuum at 45° C. for 48 h. to yield the polymer poly(IAMA/_MCPMA/α-GBLMA/ODOTMA/AAEM) (20/20/30/20/10). Mw=10,400; Mw/Mn=1.53.

Workup

  1. customwas prepared
  2. customis degassed
  3. customby bubbling with nitrogen
  4. additioncharged to a 500 ml flask
  5. customequipped with a condenser, nitrogen inlet and mechanical stirrer, along with an additional 10 g of degassed THF
  6. temperatureto reflux
  7. dissolution5 g of dimethyl-2,2-azodiisobutyrate is dissolved in 5 g of THF
  8. additioncharged in to the flask
  9. temperatureat reflux
  10. additionafter which time the reaction is diluted with 5 g of THF
  11. customThe polymer is precipitated by addition to 1.0 L of isopropanol
  12. filtrationcollected by filtration
  13. customre-precipitated
  14. dissolutionby dissolving in 50 g THF
  15. additionaddition to another 1.0 L isopropanol
  16. customcollected
  17. customdried under vacuum at 45° C. for 48 h.

Sources & evidence

ORD record
ord-e9f60006e27648abb2281cc246c25d68
Source dataset
uspto-grants-2013_12
Patent number
US08603728B2

Reaction notes

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