Page 13 - Academic Press Encyclopedia of Physical Science and Technology 3rd Organic Chemistry

P1: GLQ Revised Pages
Encyclopedia of Physical Science and Technology EN001F-4 May 7, 2001 16:19

Acetylene 65

(6-methylhept-5-en-2-one) with acetylene to yield de- C. Acetylenic Surfactants
hydrolinalool (DHL, 3,7-dimethylocta-6-en-1-yn-3-ol),
The reaction of methyl ketones such as methyl ethyl and
which is semihydrogenated to give the final product.
methyl isobutyl ketones with acetylene via base-catalyzed
DHL is an important intermediate in the commercial
ethynylation yields tertiary acetylenic diols. These com-
synthesis of vitamin A, while linalool is a key intermediate
pounds containing the 1,4-dihydroxyacetylenic grouping
in the production of vitamin E (dl-α-tocopherol). Linalool
at carbon chain lengths of eight or higher are superior
is one of the most important fragrance compounds in use
today. It is used in many perfume compositions where a CH 3 CH 3
desirable floral-rose note is desired. In the past an impor- KOH | |
2R COCH 3 + C 2 H 2 −−−→ R C C C C R
tant natural source of linalool was Brazilian rosewood. It solvent | |
has also had minor uses as a flavor ingredient. Besides OH OH
the acetylenic route, large amounts of linalool are pro-
surfactants. They are produced by Air Products and Chem-
duced by a turpentine-based intermediate, myrcene. The TM
icals, Inc., and are sold under the trademark Surfynol .
Glidden–SCM Company produces a commercial grade of Typical products are listed in the tabulation below:
linalool that is used extensively as a vitamin E intermedi-
ate. The chemistry of DHL and linalool is summarized in Trademark Generic name or description
Section XI.
Surfynol 82 3,6-Dimethyl-4-octyne-3,6-diol
Surfynol 104 2,4,7,9-Tetramethyl-5-decyne-4,7-diol
2. Citral (3,6-Dimethylocta-2,6-dienal)
Surfynol 104-A Surfynol 104 + 50% 2-ethylhexanol
The isomerization of the alkynol DHL with vanadium cat- Surfynol TG Proprietary Surfynol surfactant
alysts yields citral, an important lemonF&F compound Surfynol 440 Ethoxylated (40%) Surfynol 104
used in many F & F compositions. Citral is also used as
These surfactants, particularly Surfynols 104 and 440,
a vitamin A intermediate. Its condensation with acetone
are superior wetting–dispersing agents with very low foam
yields pseudoionone, which on cyclization (H 2 SO 4 ) forms
characteristics. They are used extensively in water-based
β-ionone, a key compound with the vitamin A ring system
industrial primers and finishes, in rinse-aid applications, in
and a valuable perfumery compound (Section XI).
pigment grinding, and in agricultural formulations. They
give synergistic performance with other surfactants in
CH 3 CH 3
| | terms of wetting and defoaming action, and in coating
CH 3 C CHCH 2 CH 2 C CHCHO
formulations they yield latex paints that can be painted
directly on oily surfaces without the finished paint crawl-
3. β-lonone [4-(2,6,6-Trimethyl-1-cyclohexen- ing or developing “fish eyes” on drying. These specialty
1-yl)-3-buten-2-one] surfactants have enjoyed steady growth since 1974, and
a 1984–1985 production estimate was 5 million pounds
Besides the acetone–citral route just described, β-ionone annually.
is made by condensing the acetylenic alcohol DHL with
diketene or methylisopropenyl ether. Both routes yield
D. Corrosion Inhibitors
pseudoionone in comparable yields. The diketene route
described in Section XI yields a tertiary acetylenic ace- Acetylenic alcohols have been used extensively since
toacetate ester as the primary product, which is then rear- the mid-1950s in oil-well acidizing operations to free
ranged with the loss of CO 2 to yield pseudoionone. The trapped oil in limestone formations. The acetylenic al-
latter compound is readily converted to β-ionone, with cohol (alkynol) is formulated with 15 to 28% HCl and
dilute sulfuric acid as catalyst. This terpenic ketone, in pumped downhole via steel tubing (N-80, J-55) to the
addition to its use in the production of vitamin A, is an limestone formation. Some acidizing operations attain
important ingredient of floral (iris) perfumes with woody depths of more than 20,000 ft with temperatures greater
notes. It also has minor uses as an ingredient in fruit than 300–400 F. The alkynols, by virtue of complexing or
◦
flavors. reactingwiththeironsurface,minimizeHClcorrosionand
CH 3 CH 3 Alkynol Chemical structure
CH CHCOCH 3
Propargyl alcohol HO CH 2 C CH
1-Hexyn-3-ol CH 3 (CH 2 ) 2 CH(OH) C CH
CH 3
4-Ethyl-1-octyn-3-ol CH 3 (CH 2 ) 3 CH(C 2 H 5 ) CH(OH) CH CH
β-Ionone OW-1 Proprietary acetylenic inhibitor