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25 "Preparation" references were found for 1 of 11 substances in CAPLUS and MEDLINE

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and is made available with permission. (C) Crown
Copyright. The French (FR) patent material in this
product/service is made available from Institut National de
la Propriete Industrielle (INPI).) for database CAPLUS
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Copyright 2003 ACS (Some records contain information from GenBank(R). See also: Benson
D.A., Karsch-Mizrachi I., Lipman D.J., Ostell J., Rapp B.A.,
Wheeler D.L. Genbank. Nucl. Acids Res. 28(1):15-18
(2000). Property values tagged with IC are from the
ZIC/VINITI data file provided by InfoChem.) for database
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Copyright 2003 ACS (Some records from 1974 to 1991 are derived from the ZIC/VINITI data
file provided by InfoChem. Some records are produced
using some INPI data from the period prior to 1986.) for
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Copyright 2003 ACS for databases CHEMCATS and CHEMLIST

Bibliographic Information

PtIV-Catalyzed Cyclization of Arene-Alkyne Substrates via Intramolecular

Electrophilic Hydroarylation. Pastine, Stefan J.; Youn, So Won; Sames, Dalibor.
Department of Chemistry, Columbia University, New York, NY, USA. Organic Letters
(2003), 5(7), 1055-1058. CODEN: ORLEF7 ISSN: 1523-7060. Journal written in
English. CAN 138:353809 AN 2003:188386 CAPLUS (Copyright 2003 ACS)

Abstract

PtCl4 was shown to be a hydroarylation catalyst with an efficiency and substrate scope
superior to previously known methods. This catalyst demonstrated consistent performance
with arene-yne substrates of diverse structural features, including propargyl ethers,
propargyl amines, and alkynoate esters, providing good to excellent yields of the 6-endo
products (chromenes, dihydroquinolines, and coumarins). In contrast, Pt(II), Pd(II), and
Ga(III) salts were shown to be sensitive to the substitution on the alkyne moiety.

Bibliographic Information

Palladium-Catalyzed Cleavage of O/N-Propargyl Protecting Groups in Aqueous

Media under Copper-Free Conditions. Pal, Manojit; Parasuraman, Karuppasamy;
Yeleswarapu, Koteswar Rao. Chemistry-Discovery Research, Dr. Reddy's Laboratories
Ltd., Hyderabad, India. Organic Letters (2003), 5(3), 349-352. CODEN: ORLEF7
ISSN: 1523-7060. Journal written in English. CAN 138:204768 AN 2003:20470
CAPLUS (Copyright 2003 ACS)

Abstract

A copper-free palladium-mediated cleavage of O/N-propargyl bonds in aq. media has been

investigated, affording a mild and convenient method for the deprotection of phenols and
anilines. The methodol. could be utilized for the selective removal of propargyl groups from
aryl ethers and amines without affecting a variety of unprotected functional groups present
in the substrates. The mechanism and scope of the reaction is discussed.

Bibliographic Information

Stereoselective synthesis of (Z)--phenoxymethylene--butyrolactones and their

sulfur analogs from 2-propynyloxy- or 2-propynylthiobenzenes. Luo, Fen-Tair; Ko,
Sheng-Li; Liu, Lijun; Chen, Hui. Institute of Chemistry, Academia Sinica, Taipei,
Taiwan. Heterocycles (2000), 53(9), 2055-2066. CODEN: HTCYAM ISSN: 0385-5414.
Journal written in English. CAN 133:350105 AN 2000:648093 CAPLUS (Copyright
2003 ACS)

Abstract

Title compds. I (X = H, F; Y = O, S; R = Me, 3,4,5-trimethoxyphenyl) and their isomers (II)

were prepd. from 2-propynyloxybenzenes and 2-propynylthiobenzenes.

O O
X Y X Y
O O

R I R II
Bibliographic Information

Cesium fluoride-mediated Claisen rearrangement of phenyl propargyl ethers:

substituent effects of an ortho-alkoxy group on the benzene ring or modified
propargyl residues. Ishikawa, Tsutomu; Mizutani, Akiko; Miwa, Chizue; Oku, Yumie;
Komano, Naoko; Takami, Atsuya; Watanabe, Toshiko. Faculty Phramaceutical Sciences,
Chiba University, Chiba, Japan. Heterocycles (1997), 45(11), 2261-2272. CODEN:
HTCYAM ISSN: 0385-5414. Journal written in English. CAN 128:61485 AN
1997:760777 CAPLUS (Copyright 2003 ACS)

Abstract

The expected 7-alkoxy-2-methylbenzofuran derivs. were effectively obtained in the cesium

fluoride-mediated Claisen rearrangement of Ph propargyl ethers with an o-alkoxy substituent
on the benzene ring. On the other hand CsF did not affect the formation of the
corresponding benzo[b]furans when ethers, carrying a propargyl residue modified by either
1,1-di-Me or 3-ethoxycarbonyl functions, were used as substrates in the rearrangement.

Bibliographic Information

Isomerization and radical polymerization of propargyl ethers in the presence of

potassium tert-butoxide. Tomita, Ikuyoshi; Yamamura, Isao; Endo, Takeshi. Res.
Lab. Res. Utilization, Tokyo Inst. Technol., Yokohama, Japan. Journal of Polymer
Science, Part A: Polymer Chemistry (1996), 34(10), 1853-1856. CODEN: JPACEC ISSN:
0887-624X. Journal written in English. CAN 125:115270 AN 1996:390271
CAPLUS (Copyright 2003 ACS)

Abstract

Radical polymns. of aryl propargyl ethers, e.g., Ph propargyl ether, 4-chlorophenyl propargyl
ether, 4-bromophenyl propargyl ether and 4-methoxyphenyl propargyl ether, were carried
out in the presence of potassium tert-butoxide. The polymers were obtained in moderate
yields from all the monomers used, whose structures and yields seemed to be irrelevant to
the substituents on arom. moieties. The present method might be applied to the polymn. of
a wide variety of isomerizable acetylenes.

Bibliographic Information

Tin Radical Addition to Alkynyl Sulfides: Reactivity of the Intermediate Thioalkyl-

Substituted -(Tributylstannyl)vinyl Radicals. Capella, Laura; Montevecchi, Pier
Carlo; Nanni, Daniele. Dipartimento di Chimica Organica A. Mangini, Universita di
Bologna, Bologna, Italy. Journal of Organic Chemistry (1994), 59(12), 3368-74.
CODEN: JOCEAH ISSN: 0022-3263. Journal written in English. CAN 121:57606 AN
1994:457606 CAPLUS (Copyright 2003 ACS)

Abstract

Ph and benzyl alkynyl sulfides, phenylalkynylamines, ethers, and selenide reacted with
tributyltin radicals to give intermediate -stannylvinyl radicals, whose fate depended on the
nature of the side chain. 4-Phenylthio-substituted but-1-en-2-yl radicals underwent
stereospecific 5-exo cyclization on the adjacent Ph ring. The resulting spirocyclohexadienyl
radicals gave thiophenes and thiopyrans by carbon-sulfur bond scission or ring expansion on
the exocyclic double bond, resp. Similar behavior was exhibited by the corresponding
selenium-contg. radical, which afforded a selenophene almost exclusively.
(Benzylthio)alkyl-substituted radicals gave products deriving from intramol. SH2 substitution
at the sulfur atom, whereas propargyl sulfides yielded a stannylallene via a -scission
reaction. No 6(or more)-membered ring closure was obsd. with pentynyl and hexynyl Ph
sulfides, which the (E)-addn. products of tin hydride oxygen- and nitrogen-contg. vinyl
radicals also gave the (E)-adducts exclusively. An interaction between the unpaired
electron orbital and the empty low-energy orbitals of the heteroatom might explain why
sulfur and selenium can undergo 5-exo cyclization.

Bibliographic Information

Alkyliron and alkylcobalt reagents. VII. On the substitution of the halogen of

alkenyl chlorides, alkenyl fluorides, and alkynyl halides by reagents of the type
R4MLi2(M = iron, cobalt). Kauffmann, Thomas; Saelker, Reiner; Voss, Karl Uwe.
Org.-Chem. Inst., Univ. Muenster, Muenster, Germany. Chemische Berichte (1993),
126(6), 1447-52. CODEN: CHBEAM ISSN: 0009-2940. Journal written in German.
CAN 119:159362 AN 1993:559362 CAPLUS (Copyright 2003 ACS)

Abstract

Me4FeLi2 and Me4CoLi2, which are favorable reagents for the substitution of Br in alkenyl
bromides, also proved to be favorable for the substitution of the halogen in alkenyl chlorides
(yields 68-99%; nearly complete retention of configuration in the case of Me4FeLi2), -
fluorostyrene (best yield 92%), and 1-fluoronaphthalene (best yield 47%). Me4FeLi2
differentiates between various alkenyl chlorides in 1:1 competition expts. better than
Me4CoLi2 and is the optimal reagent for the substitution of halogen in 1-chloro-2-phenyl-
ethyne, 1-bromo-2-phenylethyne, and 1-chloro-3-phenoxypropyne by Me (yields 70%, 46%,
and 80%, resp.). Substitution of the halogen in 1-chloro-2-phenyl-ethyne, by the Bu, octyl,
and Ph residue is better achieved by the catalytic systems RMgBr + 2.5 mol% FeCl2 (R = Bu,
octyl, Ph; yields 75%, 63%, and 96%, resp.) than by the reagents Bu4FeLi2, Bu4Fe(MgBr)2,
Oct4Fe(MgBr)2, or Ph4Fe(MgBr)2 (yields 18-28%).

Bibliographic Information

Studies on curing reaction of maleimide resins. VI. The reaction between N-

phenylmaleimide and propargyl compounds. Enoki, Takashi; Yazawa, Hidemi; Ishii,
Keiichiro; Yamamoto, Takahisa. Fundam. Res. Lab., Sumitomo Bakelite Co., Ltd.,
Yokohama, Japan. Netsu Kokasei Jushi (1992), 13(2), 80-8. CODEN: NKJUDH ISSN:
0388-4384. Journal written in Japanese. CAN 118:148648 AN 1993:148648
CAPLUS (Copyright 2003 ACS)

Abstract

Propargyl Ph ether (I) and its chromenizated product at 175, i.e., -chromene (II), were
reacted with N-phenylmaleimide (III). In the former case, a 1:2 adduct of I with III was
formed independent of the catalysts used. In the latter, oligomers were mainly formed.
Without catalyst, a 1:1 II-IIII adduct of mol. wt. 275 was also formed. These products were
analyzed by FD-MS, NMR, gel-permeation chromatog., and CHN-elemental anal. Based on
the NMR data, the chem. structures were discussed.

Bibliographic Information

The synthesis and regioselectivity of elimination of some 1,3-difunctional

sulfoxides [Erratum to document cited in CA114(23):228452g]. Khan, M. Akram.
Dep. Chem., Univ. Kuwait, Safat, Kuwait. Journal of Chemical Research, Synopses
(1991), (6), 163. CODEN: JRPSDC ISSN: 0308-2342. Journal written in English.
CAN 115:114076 AN 1991:514076 CAPLUS (Copyright 2003 ACS)
Abstract

An error in structure II has been cor. The error was not reflected in the abstr. or the index
entries.

Bibliographic Information

The synthesis and regioselectivity of elimination of some 1,3-difunctional

sulfoxides. Khan, M. Akram. Dep. Chem., Univ. Kuwait, Safat, Kuwait. Journal
of Chemical Research, Synopses (1991), (3), 62-3. CODEN: JRPSDC ISSN: 0308-2342.
Journal written in English. CAN 114:228452 AN 1991:228452 CAPLUS (Copyright
2003 ACS)

Abstract

1,3-Difunctional sulfoxides, RCH2CH(SOPh)CH2R1 [I, R = SPh, 4-BrC6H4S, SEt, OEt, etc.; R1

= CH(CO2Et)2, OCH2Ph, NEtPh, etc.] were prepd. and undergo thermal elimination to give
either RCH:CHCH2R1 or RCH2CH:CHR1. Thus, condensation of (EtO2C)2CH2 with
[Link].CCH2Br gives [Link].CCH2CH(CO2Et)2 which reacts with 1-cyano-2-
(phenylsulfinyl)ethane to give CH2:CH(SOPh)CH2CH(CO2Et)2 which is treated with PhSH to
give I [R = SPh, R1 = CH(CO2Et)2] (II). II underwent thermolysis to give 69% (Z)- and (E)-
PhSCH:CHCH2CH(CO2Et)2 as a 44:56 mixt.

Bibliographic Information

A facile synthesis of aryl ethers of ethynyl-carbinols using the Mitsunobu reaction.

Subramanian, R. Sankara; Balasubramanian, K. K. Dep. Chem., Indian Inst. Technol.,
Madras, India. Synthetic Communications (1989), 19(7-8), 1255-9. CODEN: SYNCAV
ISSN: 0039-7911. Journal written in English. CAN 112:178193 AN 1990:178193
CAPLUS (Copyright 2003 ACS)

Abstract

The synthesis of aryl ethers of ethynyl carbinols using the Mitsunobu reaction is reported.
Thus, a mixt. of [Link].CCMe2OH and 4-MeC6H4OH in C6H6 was treated with Ph3P and
EtO2CN:NCO2Et to give 55% [Link]. Eleven similar examples are
also reported.

Bibliographic Information

Preparation of aromatic allene compounds. Yamada, Mitsuo; Kayano, Hiromichi;

Aoki, Kei; Ishii, Keizou. (Nippon Paint Co., Ltd., Japan). Eur. Pat. Appl. (1989), 29 pp.
CODEN: EPXXDW EP 333445 A2 19890920 Designated States R: DE, GB. Patent
written in English. Application: EP 89-302519 19890315. Priority: JP 88-61119; JP
88-61120; JP 88-61121; JP 88-61122; JP 88-61123. CAN 112:157847 AN
1990:157847 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date

EP 333445 A2 19890920 EP 1989-302519 19890315
EP 333445 A3 19911211
EP 333445 B1 19950118
R: DE, GB
JP 01233250 A2 19890919 JP 1988-61119 19880315
JP 2532270 B2 19960911
JP 01233251 A2 19890919 JP 1988-61120 19880315
JP 2532271 B2 19960911
JP 01233252 A2 19890919 JP 1988-61121 19880315
JP 07045422 B4 19950517
JP 01233259 A2 19890919 JP 1988-61122 19880315
JP 06021106 B4 19940323
JP 01233253 A2 19890919 JP 1988-61123 19880315
US 5340931 A 19940823 US 1989-323786 19890315

Priority Application Information

JP 1988-61119 19880315
JP 1988-61120 19880315
JP 1988-61121 19880315
JP 1988-61122 19880315
JP 1988-61123 19880315

Abstract

Title compds. (H[Link]HO)nRAm [R = (un)substituted C6H6, naphthalene, anthracene,

azobenzene, bisphenol, polyphenyl (2-10 benzene rings connected in line), PhR1Ph (Ph =
(un)substituted phenylene; R1 = C1-6 aliph. or alicyclic, the chain optionally interrupted by 1
or more O); A = HO2C, HO3S, H[Link]H; m = 0-3; n = 1-10] useful as reactive monomers for
prepn. of vinyl resins (no data) are prepd. 1-Naphthol, NaOH, Bu4N+Br- and
[Link] were condensed to give 63.6% 1-(propargyloxy)naphthalene which was
treated with Me3COK in Me3COH at 50 to give 1-allenyloxynaphthalene.

Bibliographic Information

Preparation of tert-butylakynols as agrochemical intermediates. Smuda, Hubert;

Rohr, Wolfgang. (BASF A.-G., Fed. Rep. Ger.). Ger. Offen. (1989), 7 pp. CODEN:
GWXXBX DE 3800306 A1 19890720 Patent written in German. Application: DE
88-3800306 19880108. CAN 112:54972 AN 1990:54972 CAPLUS (Copyright 2003
ACS)

Patent Family Information

Patent No. Kind Date Application No. Date

DE 3800306 A1 19890720 DE 1988-3800306 19880108
EP 324191 A1 19890719 EP 1988-121928 19881231
R: BE, CH, DE, ES, FR, GB, IT, LI, NL
US 4997989 A 19910305 US 1989-293447 19890104
JP 01213250 A2 19890828 JP 1989-1408 19890109

Priority Application Information

DE 1988-3800306 19880108

Abstract

[Link](OH)CMe3 [I; R = H, C1-4 (halo)alkyl, C1-4 alkoxy, aryl,

aryloxy, PhCH2, halo; n = 1-5; when n > 1, R may be the same or different], useful as
intermediates for prepn. of 1,2,4-triazole fungicides and plant growth regulators, are prepd.
by condensation of [Link] (II) with Me3CCHO in the presence of a
base, preferably KOH, in a dipolar, aprotic solvent. Thus, PhOH was etherified with
[Link] to give 87% II (Rn = H) which was condensed with Me3CCHO in THF
contg. 1 equiv KOH at 50 to give 92% I (Rn = H). The latter was oxidized to the ketone with
K2Cr2O7 (60%) and hydrogenated over Pd/C to give 89% PhO(CH2)COEt, which can be
converted to triazoles by known methods.

Bibliographic Information

3-Phenoxy-2-(phenylsulfinyl)prop-1-ene and 3-bromo-2-(phenylsulfinyl)prop-1-

ene. Synthons for N-alkylated cyclic enamides. Khan, M. Akram; Al-Saleh, Balkis.
Dep. Chem., Univ. Kuwait, Safat, Kuwait. Journal of Chemical Research, Synopses
(1989), (2), 30-1. CODEN: JRPSDC ISSN: 0308-2342. Journal written in English.
CAN 111:214368 AN 1989:614368 CAPLUS (Copyright 2003 ACS)

Abstract

Cyclocondensation reaction of PhS(O)C(:CH2)CH2NHR (I; R = CH2Ph, p-tolyl, cyclohexyl) with

(EtO2C)2CHNa gave mainly or exclusively carbethoxypiperidinones II. Thermolysis of II in
PhMe led to regiospecific elimination of PhSOH and gave 70-75% title enamides III. I were
prepd. from the title compds. in 68-100% yields.

S(O)Ph

NR NR
EtO 2 C EtO 2 C
O II O III

Bibliographic Information

Selenium heterocycles. XXXV. Synthesis and pyrolysis of aryloxy-, arylthio-, and

arylseleno-1,2,3-selenadiazoles. Shafiee, A.; Toghraie, S.; Aria, F.; Mortezaei-
Zandjani, G. Coll. Pharm., Tehran Univ., Teheran, Iran. Journal of Heterocyclic
Chemistry (1982), 19(6), 1305-8. CODEN: JHTCAD ISSN: 0022-152X. Journal written
in English. CAN 98:143345 AN 1983:143345 CAPLUS (Copyright 2003 ACS)

Abstract

Selenadiazoles I (X = S, Se; R = Me, Ph; R1 = Ph, PhCH2, 4-BrC6H4, 4-ClC6H4, 4-MeC6H4)

and aryloxymethyl-1,2,3-selenadiazoles II (R2 = H, Me, Cl) were synthesized. Pyrolysis of
these compds. gave acetylenes [Link].CXR1 and [Link], resp.
Oxidn. of I (X = S) with 3-ClC6H4C(O)O2H gave I [X = S(O), SO2].
 N N
N N
Se Se
R R2 OCH 2
XR 1 I II

Bibliographic Information

Cleavage of primary and secondary acetylenic alcohols. Vereshchagin, L. I.;

Buzilov, S. R.; Bol'shedvorskaya, R. L.; Kirillova, L. P. Inst. Nefte- Uglekhim. Sint.,
Angarsk, USSR. Zhurnal Organicheskoi Khimii (1976), 12(6), 1165-9. CODEN:
ZORKAE ISSN: 0514-7492. Journal written in Russian. CAN 85:93980 AN
1976:493980 CAPLUS (Copyright 2003 ACS)

Abstract

Treatment of [Link].CCHR1OH(R, R1 given; H, Ph; Ph, Ph; Ph, Pr; CHPhOH, Ph; Ph,
[Link]; 1-hydroxycyclohexyl, 1-hydroxycyclohexylacetylenyl; Bu, 1-hexynyl; PhOCH2,
[Link].C) with -MnO2 and KOH cleaved the alc. and gave [Link] and
R1CO2K. Cleavage of 18 R([Link].C)nCH2OH (I; R = e.g., Bu, Br, Ph, Bu2NCH2; n =
1,2,3) gave R([Link].C)nH and HCO2K. Several I were prepd.

Bibliographic Information

Reaction of picryl azide with aryloxyallenes. Boerresen, Steinar; Crandall, Jack K.

Dep. Chem., Indiana Univ., Bloomington, IN, USA. Journal of Organic Chemistry
(1976), 41(4), 678-81. CODEN: JOCEAH ISSN: 0022-3263. Journal written in English.
CAN 84:90080 AN 1976:90080 CAPLUS (Copyright 2003 ACS)

Abstract

The reaction of aryloxyallenes I (R, R4 = H, Cl, Me; R1, R2, R3 = H, Cl) with 2,4,6-
(O2N)3C6H2N3 gives two types of isolated adducts, II and III. The reaction proceeded via
formation of the unisolated triazoline which, undergo an exceptionally facile Claisen
rearrangement to yield the adducts of structure III, which unless blocked by a substituent at
R5 rapidly tautomerize to the isomeric adducts II.

Bibliographic Information

Organic hydrogen getters. II. Preparation and properties of phenyl propargyl

ether and 1,6-diphenoxy-2,4-hexadiyne (DPPE). Courtney, R. L. Sandia Lab.,
Albuquerque, NM, USA. Avail. Dep. NTIS. Report (1974), (SLA-73-1094), 13 pp.
From: Nucl. Sci. Abstr. 1974, 30(1), 2287. Report written in English. CAN 83:27769
AN 1975:427769 CAPLUS (Copyright 2003 ACS)

Abstract

Phenyl propargyl ether was prepd. via a Williamson reaction between potassium phenoxide
and propargyl chloride. The product, a colorless liq., was used to prep. 1,6-diphenoxy-2,4-
hexadiyne by oxidative coupling in pyridine with a copper(I) chloride catalyst. Both
products structures were verified by their Raman and infrared spectra. Thermal stability of
the diphenyl ether was examd. with differential scanning colorimetry and thermogravimetric
anal.

Bibliographic Information

Synthesis and hydraton of propargyl ethers and ethynylation of the resulting

ethers of hydroxyacetone. Vartanyan, R. S.; Kazaryan, Zh. V.; Kucherov, V. F. Inst.
Tonkoi Org. Khim. im. Mndzhoyana, Erevan, USSR. Armyanskii Khimicheskii Zhurnal
(1974), 27(4), 295-303. CODEN: AYKZAN ISSN: 0515-9628. Journal written in Russian.
CAN 81:77405 AN 1974:477405 CAPLUS (Copyright 2003 ACS)

Abstract

[Link] (I; R = Me, Et, Me2CH, Pr, Bu, Ph, p-tolyl, p-MeO2CC6H4, PhCH2, Ph2CH,
H2C:CHCH2, Ac, NCCH2CH2, [Link].CCH2) were prepd. (45-91%) by reaction of
[Link].CCH2OH with RX (X = halo) in the presence of KOH in Me2SO or cyclohexanone.
Hydration of I gave 42-80% ROCH2COMe (II; R = Me, Et, Me2CH, Ph, p-tolyl, p-MeO2CC6H4,
PhCH2, H2C:CHCH2, NCCH2CH2, Ac). Condensation of II with [Link](R1 =
H2C:CMe, H2C:CH, H, Me2C(OH)CH2, allyl, vinyl, 1-cyclohexenyl) gave 23-80%
[Link](OH)CH2OR.

Bibliographic Information

Silver ion catalyzed rearrangement of propargyl phenyl ether. Koch-Pomeranz,

Ursula; Hansen, Hans Jurgen; Schmid, Hans. Org. Chem. Inst., Univ. Zurich, Zurich,
Switz. Helvetica Chimica Acta (1973), 56(8), 2981-3004. CODEN: HCACAV ISSN:
0018-019X. Journal written in German. CAN 81:77243 AN 1974:477243 CAPLUS
(Copyright 2003 ACS)

Abstract

Propargyl Ph ethers formed -complexes of the triple bond with Ag+ catalysts and the
complexes underwent [3s,3s]-sigmatropic rearrangements to give allenyldienones (e.g., I),
which then rearranged to 3-allenylphenols (e.g., II) or, if the ortho position was free, to
nonisolated 2-allenylphenols, which further rearranged to 2H-chromenes (e.g., 3,5-
[Link] gave III). CHCl3 as solvent favored 2H-chromene formation,
while C6H6 favored formation of benzofurans or allenylphenols.

Bibliographic Information

Influence of structure on the rate of thermal rearrangement of aryl propargyl

ethers to the chromenes. Gem-dimethyl effect. Harfenist, Morton; Thom, Edna.
Burroughs Wellcome Co., Research Triangle Park, NC, USA. Journal of Organic
Chemistry (1972), 37(6), 841-8. CODEN: JOCEAH ISSN: 0022-3263. Journal written
in English. CAN 76:126142 AN 1972:126142 CAPLUS (Copyright 2003 ACS)

Abstract

The rates of first-order thermal cyclizations of a group of para-substituted aryl propargyl

ethers [Link] (R, R1 = H or Me) was detd. in 0-Cl2C6H4 as a function
of Z (OMe, NHAc, H, Cl, CN, NO2) and of the number of Me groups. Where R and R1 are
both H (k values extrapolated to 189.8) or where R was Me and R1 was H (k values
extrapolated to 161.6), the points followed an adequate Hammett relation using + ( = -
0.43) although the NO2 and CN did not give a good fit for R = R1 = H, and p-Cl was faster
than p-H for R = H, R1 = Me. The attempted Hammett plot for the gem-dimethyl analogs R
= R1 = Me had a paraboloid shape, e.g., X = NHAc and X = NO2 had about the same rate,
with X = H at a min. (k values extrapolated to 161.6). The S.++. and H.++. followed no
obvious order. The results are best explained by assuming that the gem-dimethyl effect
results from an increase in the proportion of the rotamer with the ethynyl group positioned
near the benzene ring, i.e., the rotamer best positioned for reaction, when no H is available
to rotate to that position, and that activation of the position meta to the substituent Z, at
least by the electron-withdrawing groups, exists. Preparative runs showed that an
essentially quant. yield of 2-methyl or 2,2-dimethyl-3-chromenes could be obtained.

Bibliographic Information

Aryl 2-propynyl ethers or thio ethers as synergists for acaricidal and insecticidal
carbamic acid derivatives. Martin, Henry; Dittrich, Volker; Pissiotas, Georg; Rohr, Otto.
(CIBA-Geigy A.-G.). Ger. Offen. (1971), 46 pp. CODEN: GWXXBX DE 2100325
19710715 Patent written in German. Application: DE 71-2100325 19710105. CAN
75:151523 AN 1971:551523 CAPLUS (Copyright 2003 ACS)

Patent Family Information

Patent No. Kind Date Application No. Date

DE 2100325 A 19710715 DE 1971-2100325 19710105
CH 528858 A 19721015 CH 1970-528858 19700108
FR 2074501 A5 19711001 FR 1970-47449 19701231
ZA 7100046 A 19711027 ZA 1971-46 19710105
GB 1327742 A 19730822 GB 1971-476 19710105
US 3777024 A 19731204 US 1971-104143 19710105
NL 7100180 A 19710712 NL 1971-180 19710107
AT 304167 B 19721227 AT 1971-83 19710107

Priority Application Information

CH 1970-205 19700108

Abstract

Activities of com. biocides such as Malathion, Rotenone, Chlorphenamidine (I) Dicrotophos

(II), etc. are greatly increased in the presence of 0.001-200 parts of III (X=O, S; R=H,
halogen, C1-7 alkyl; R1, R2, R3, R4, R5=H, halogen, C1-7 alkyl or alkoxy, NO2, or
methylenedioxy). Thus, the mortality rate against female houseflies was 6% for II, 0% for III
(X=O; R=R1=R4=H; R2=R3=R5=Cl) (IV) and 40% for a mixt. of equal parts II and IV.
Similarly an emulsion contg. 50 ppm I and 50 ppm III (X=O; R=R1=R4=R5=H; R2=Me;
R3=Cl) was twice as effective against Tetranychus telarius as one contg. 100 ppm of I alone.
2,4,5-Trichlorophenol was refluxed with propargyl bromide, CaCO3, and acetone to give IV,
m. 60-1. Seventy-four other III were also prepd.

Bibliographic Information

Reactions of unsaturated esters of aromatic sulfonic acids. II. Alkylating

properties of unsaturated esters of aromatic sulfonic acids. Vizgert, R. V.;
Sendega, R. V. L'vov. Politekh. Inst., Lvov, USSR. Zhurnal Organicheskoi Khimii
(1969), 5(3), 488-92. CODEN: ZORKAE ISSN: 0514-7492. Journal written in Russian.
CAN 71:12238 AN 1969:412238 CAPLUS (Copyright 2003 ACS)

Abstract
The reactivity was studied of PhSO3Y (I) (Y is H2C:-CMeCH2, H2C:CHCH2, or
[Link].CCH2 in the reactions with nucleophilic reagents: EtOK, PhOK, PhSK, o-
MeC6H4SK, K tert-dodecylmercaptide, or KSCN. Also the reactions of
XC6H4SO3CH2CH:CH2 (X is p-Me, H, or m-NO2) were studied with PhSK. The yields of the
alkylation products (YOEt, YOPh, YSPh, YSC6H4Me-o, YSCN, etc.) depended on Y and to a
much lesser extent on the nature of the nucleophile. The yields decreased in series
H2C:CMeCH2 > H2C:CHCH2 > [Link].CCH2. The same reactivity order was found (R. V.
Vizgert, 1968) in the sapon. of I. Thus I, which are easier to sapon., are also better
alkylating agents.

Bibliographic Information

Insecticides. (Hoffmann-La Roche, F., und Co., A.-G.). Neth. Appl. (1967), 27
pp. CODEN: NAXXAN NL 6612645 19670309 Patent written in Dutch. Application:
NL 66-12645 19660908. CAN 68:68708 AN 1968:68708 CAPLUS (Copyright 2003
ACS)

Patent Family Information

Patent No. Kind Date Application No. Date

NL 6612645 A 19670309 NL 1966-12645 19660908
US 3489805 A 19700113 US 1965-485904 19650908
US 3362871 A 19680109 US 1965-486545 19650910
US 3423428 A 19690121 US 1966-531371 19660303
IT 986752 A 19750130 IT 1966-20643 19660908
US 3804905 A 19740416 US 1972-232244 19720306

Priority Application Information

US 1965-485904 19650908
US 1965-485911 19650908
US 1965-485922 19650908
US 1965-485934 19650908
US 1965-485951 19650908
US 1965-486545 19650910
US 1966-531371 19660303
US 1965-433209 19650216
US 1969-828731 19690528

Abstract

Synergetic insecticides contain an insecticidal carbamate, and a propargyl aryl ether of the
general formula, [Link] (Ia), where Aris an aromatic group, Y is O or S, and X is
halogen. Preferably used are the di- and trihalo-, and mononitrophenyl propargyl ethers,
e.g., 2,4-dichlorophenyl propargyl ether [3-(2,4-dichlorophenoxy)-1-propyne]. The useful
concn. is 0.1-10 wt. parts propargyl ether, and 1 wt. part carbamate. The insecticides are
active against various insects, e.g., Diptera (Drosophila melanogaster), Lepidoptera
(Trichoplusia ni), and Coleoptera (Hypera postica). The synergetic action has been examd.
on Musca domestica. The propargyl aryl ethers were prepd. by reaction of ArYH, and a 3-
halo-1-propyne to give [Link], which is halogenated to give
[Link]. Thus, 3-(2,3,4-trichlorophenoxy)-1-propyne (I) was obtained by
refluxing while stirring 8 hrs. 13.5 g. 2,3,4-trichlorophenol, 8.9 g. 3-bromo-1-propyne, 10.4 g.
K2CO3, and 125 ml. acetone to give I, m. 78-80 (EtOH). Similarly prepd. were the following
Ia (ArY, X, and m.p. or b.p./mm. given): 2,3,6-trichlorophenoxy, H, 63-5; 3,4,5-
trichlorophenoxy, H, 64-5; 2,4,5-trichlorophenoxy, I, 63-4; 2,4,6-trichlorophenoxy, H, 99-
100; 2,3,5-trichlorophenoxy, H, 62; 2,3-dichlorophenoxy, H, 47-9; 4-methoxyphenoxy, H,
118-20/7; 3-nitrophenoxy, H, 114-16; 3-nitrophenoxy, H, 67-9; 2-nitro-4-chlorophenoxy, H,
82-4; 2,4-dibromophenoxy, H, 67.2-7.8; 2,4-dichloro-1-naphthyloxy, H, 100-100.8; 2-
nitrophenoxy, H, 74-6; 3-methyl-6-isopropylphenoxy, H, 69/4; 4-chloro-6-iodo-2-
nitrophenoxy, H, 91-3; 2,3-dibromophenoxy, H, 49-50; phenoxy, H, 95/25. To prep. 1-iodo-
3-(2,3,6-trichlorophenoxy)-1-propyne (II), 19.8 g. 2,3,6-trichlorophenol, 13.1 g. 3-bromo-1-
propyne, 15.2 g. K2CO3, and 150 ml. acetone were refluxed with stirring 8 hrs. The
recrystd. 3-(2,3,6-trichlorophenoxy)-1-propyne (8.5 g.) (m. 63-5) was mixed with 75 ml.
ethanol, and while stirring at the same time, 12 g. iodine, in small portions, and 45 ml. 10%
aq.
NaOH, dropwise for 15 min. (temp. held at 20-5), were added. After 1 hr. stirring at room
temp. the mixt. was dild. with 100 ml. H2O and cooled in ice-water to give II, m. 88-9.
Similarly prepd. were the following Ia (X = I; ArY and m.p. or b.p./mm. given): 2,4,5-
trichlorophenoxy, 111-13; 2,3,5-trichlorophenoxy, 98-100; 2,3,4-trichlorophenoxy, 107-10;
3,4,5-trichlorophenoxy, 107-10; 2,4,6-trichlorophenoxy, 102; 2,3-dichlorophenoxy, 59-60;
2,5 iodochlorophenoxy, 86-8; 2,3,4,6-tetrachlorophenoxy, 104-5; 2,3,4,5,6-
pentachlorophenoxy, 140-1; 4-methoxyphenoxy, 44-5; 2,3-dichlorophenoxy, 68-9; 2-
nitrophenoxy, 96-8; 2-nitro-4-chlorophenoxy, 116-17; 3-nitrophenoxy, 88-90; 3-phenoxy,
90/0.05; 4-fluorophenoxy, 87/0.075; 2-chlorophenoxy, 97/0.03; 2-nitro-4-chloro-6-
iodophenoxy, 115-16. 4,2-Cl(O2N)C6H3SH (20 g.) in 55 cc. 10% aq. NaOH was treated
dropwise, with stirring at 25-30, with 13 g. [Link] and the mixt. stirred 1 hr. at
room temp. to give 3-(2-nitro-4-chlorophenylthio)-1-propyne, m. 134-6. Similarly prepd.
were the following Ia (X = H, Y = S; Ar and m.p. or b.p./mm. given): 2,3-Cl2C6H3, 59-60;
3,4-Cl2C6H3, 98/0.04; 2,4,5-Cl3C6H2, 76-7. Analogous to the prepn. of II was prepd. Ia (Ar
= 2,3-Cl2C6H3, X = I, Y = S), m. 72-4.

Bibliographic Information

Preparation of proparglyic, allenic, and acetylenic derivatives of the elements of

Group VI B. Pourcelot, Guy; Cadiot, Paul. Lab. Rech. Chim Org., Paris, Fr.
Bulletin de la Societe Chimique de France (1966), (9), 3016-24. CODEN: BSCFAS ISSN:
0037-8968. Journal written in French. CAN 66:94770 AN 1967:94770 CAPLUS
(Copyright 2003 ACS)

Abstract

[Link].CCH2Br (100 ml.) and 1.3 moles PhONa in 800 ml. abs. EtOH was refluxed 4.5
hrs. and poured into 1 l. H2O. Extn. with pentane, washing with 20% aq. NaOH, and distn.
gave 88% [Link], b15 87. Similarly prepd. were 56%
[Link], b16 86, and 82% [Link], b0.5 65. To 50 g. EtSH
and 0.7 mole EtONa in 0.5 l. abs. EtOH was added dropwise a soln. of 80 g.
[Link].CCH2Br in 50 ml. EtOH, keeping the temp. of the mixt. <30. After 3-4 hrs. at
room temp., the soln. was poured into 2 l. H2O contg. 10 ml. HCl, extd. with pentane,
washed with aq. NaHCO3 and distd. to yield 76 [Link], b76 66-7. Similarly
prepd. were 80% [Link], b0.5 71; 80.5% [Link], b28 65;
88.5% [Link], b0.5 128; 75% [Link], b3 121; 78%
[Link], b0.3 73; 80% BrNH2:C(NH2)[Link], m. 122 (pptd. from
Me2CO by pentane); 81% [Link], b1 170; 78% [Link], b2
109; 88% [Link], b0.5 95; 80% [Link], b0.5 72; 82%
[Link], b1 102 and 40% [Link].CCH2SCH2CO2H, m. 57
(cyclohexane). To 23 g. Na2S in 60 ml. H2O was added a solution of 59.5 g.
[Link].CCH2Br in 100 ml. EtOH as in the preceding method to yield 68%
([Link].CCH2)2S, b15 54-5. A soln. of 7.6 g. thioacetic acid in 20 ml. EtOH was added
to a soln. of 4.7 g. NaOH in 80 ml. H2O and the mixt. added dropwise to a soln. of 12 g.
[Link].CCH2Br in 20 ml. EtOH at 30. The mixt. was heated 1 hr. at 50, extd. with
ether and distd. to yield 57% [Link], b15 51.5-2.5. To a soln. of 2.3 g. Na in
800 ml. abs. EtOH was added 11 g. PhOH and 6.15 g. [Link].CCH2Cl and the mixt.
refluxed 2 hrs. and poured into 1 l. H2O. Extn. with CCl4, washing with 20% aq. NaOH and
distn. gave 76% [Link].CCH2OPh, b0.01 145. Similarly prepd. were 74%
[Link].CCH2SPh, m. 45 (EtOH); 78% [Link].CCH2SEt, b2 115 and,
65% [Link].CCH2SePh, m. 33 (EtOH).
With strong bases RMC(R")[Link]' .dblharw. RMC(R"):C:CR' and
[Link]' .dblharw. RMCH:C:CHR' .dblharw. [Link].CCH2R' (M = O, S, Se)
with rate and extent of isomerization increasing with base strength and depending on M (S >
Se > O), R (Ar > R), R" (H > Me), and R' (R, Ar > H). [Link]' gives only the
allene. Thus, a soln. of 7.9 g. [Link] in 60 ml. 0.1 N tert-BuOK in tert-BuOH
was heated 1 hr. at 7 and added to a mixt. of 200 ml. 0.2N NaOH in EtOH and 50 ml. 2N K
iodomercurate, kept 10 min. and filtered. The filtrate was dild. with 3-4 times its vol. of
H2O. Extn. with pentane and distn. gave 67.5% PhOCH:C:CH2, b35 98. Similarly prepd.
were 65% PhOCH:C:CHMe, b2 52, and 72% PhSeCM[Link]H2, b2 84. When M = S, Se the
isomerization may be stopped at the allene, thus: 22.2 g. [Link] at 52 was
added to 150 ml. 0.1N EtONa in EtOH at 52 and held at this temp. 5.5 min., then worked up
as in the preceding method to give 46% PhSCH:C:CH2, b0.1 68. Similarly prepd. (70, 12
min.) were 43% EtSCH:C:CH2, b55 54 and (48, 70 min.) 58.5% PhSeCH:C:CH2, b0.5 70. A
soln. of 8.7 g. [Link] in 50 ml. tetrahydrofuran was stirred with 11.75 g. dry
KOH at room temp. for 15 min. and treated as in the preceding two methods to give 67%
PhSCM[Link]H2, b0.1 59. Similarly prepd. were 90% [Link] (room temp., 1 hr.),
b1 82; (55, 30 min.), 66% [Link], b105 75; (room temp., 3 hrs.) 67%
[Link] b35 69; and (room temp., 3 hrs) 72% [Link], b0.8
134. A soln. of 10 g. [Link] in 50 ml. 0.1N tert-BuOK in tert-BuOH was
heated 1 hr. at 85 and added to a mixt. of 100 ml. 0.2N NaOH in EtOH and 15 ml. 2N aq. K
iodomercurate. Extn. with pentane gave a mixt. of 86-8% [Link] and 12-4%
PhSeCH:C:CH2, b3 90-2. Gas-liquid chromatography on diethylene glycol succinate at 155-
60 gave 45% [Link], b0.5 77.