Triethylamine → HCID 86754047, compound

HRID 443094Notes

Reaction equation

HRID 443094 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][Si:5]1([CH3:19])[O:12][Si:11]([CH3:14])([CH3:13])[O:10][Si:9]([CH3:16])([CH3:15])[O:8][Si:7]([CH3:18])([CH3:17])[O:6]1.C(N(CC)CC)C.[F:27][C:28]([C:63]([F:66])([F:65])[F:64])([O:32][C:33]([F:62])([F:61])[C:34]([F:60])([C:56]([F:59])([F:58])[F:57])[O:35][C:36]([F:55])([F:54])[C:37]([F:53])([C:49]([F:52])([F:51])[F:50])[O:38][C:39]([F:48])([F:47])[C:40]([F:46])([F:45])[C:41]([F:44])([F:43])[F:42])[C:29](F)=[O:30]>>[F:27][C:28]([C:63]([F:64])([F:65])[F:66])([O:32][C:33]([F:61])([F:62])[C:34]([F:60])([C:56]([F:57])([F:58])[F:59])[O:35][C:36]([F:54])([F:55])[C:37]([F:53])([C:49]([F:50])([F:51])[F:52])[O:38][C:39]([F:48])([F:47])[C:40]([F:46])([F:45])[C:41]([F:44])([F:43])[F:42])[C:29]([O:1][CH2:2][CH2:3][CH2:4][Si:5]1([CH3:19])[O:12][Si:11]([CH3:14])([CH3:13])[O:10][Si:9]([CH3:16])([CH3:15])[O:8][Si:7]([CH3:18])([CH3:17])[O:6]1)=[O:30]

Participants

4

Reactant 3

HCID 8471TriethylamineHCID 119616Perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluorideHCID 22677161HCID 22677161, compound

Product 1

HCID 86754047HCID 86754047, compoundYield 66%

Procedure

A 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel was charged with 7.7 g of 98% (3-hydroxypropyl)heptamethylcyclotetrasiloxane (22 mmoles) and 2.3 g of triethylamine (23 mmoles). The mixture was stirred and 15.0 g of 97% perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl fluoride (21.9 mmoles) was added dropwise. After complete addition of the acid fluoride a gas chromatographic analysis indicated that essentially all of the acid fluoride and most of the cyclosiloxane were consumed with predominately the formation of one product. A 25 mL portion of dilute hydrochloric acid was added to the flask and the two phase mixture was transferred into a separatory funnel and the aqueous layer separated from the siloxane layer. The siloxane layer was washed with two 25 mL portions of water and the siloxane layer was transferred into a 50 mL round bottom flask and distilled at 110° C. and 0.3 mm Hg to yield a fraction of 14.7 g (66% yield) of 97% [3-(perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl)oxypropyl]heptamethylcyclotetrasiloxane (14.3 mmoles), which corresponds to formula (I) wherein m is 1, n is 3, X is OC(O), and RF is given by formula (II) wherein p is 3, or more specifically as shown in formula (VII) below wherein p is 3. The product was analyzed by spectroscopy with the following results: 1H NMR 400 MHz, CDCl3 : d 0.1 (s 21 H), 0.6 (t 2 H), 1.8 (p 2 H), 4.4 (m 2 H); 19F NMR 376 MHz, CDCl3 : d -81 (CF3), -82 (CF3), -83 (CF3), -85 (CF3), -130 (CF2), -132 (CF2), -144 (CF); IR (neat liquid on NaCl): cm-1 : 2970 (m), 1780 (s), 1245 (vs), 1200 (s), 1145 (s), 1070 (vs), 995 (s), 970 (s), 810 (vs), 750 (m). ##STR8##

Workup

  1. customA 50 mL round bottom flask equipped with a magnetic stirring bar and an addition funnel
  2. custommost of the cyclosiloxane were consumed with predominately the formation of one product
  3. additionA 25 mL portion of dilute hydrochloric acid was added to the flask
  4. customthe two phase mixture was transferred into a separatory funnel
  5. customthe aqueous layer separated from the siloxane layer
  6. washThe siloxane layer was washed with two 25 mL portions of water
  7. customthe siloxane layer was transferred into a 50 mL round bottom flask
  8. distillationdistilled at 110° C.

Sources & evidence

ORD record
ord-01f05b251f6747cfb131fce9b77ce510
Source dataset
uspto-grants-1999_04
Patent number
US05892086

Reaction notes

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