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5 Research Topic candidates were identified in CAPLUS and MEDLINE.
using the phrase "polymerization of citral"
Selected 3 of 5 candidate topics.
1 reference was found containing "polymerization of citral" as entered.
15 references were found containing the two concepts "polymerization" and "citral" closely associated with one
another.
61 references were found where the two concepts "polymerization" and "citral" were present anywhere in the
reference.
Copyrights:
Copyright 2003 ACS (The UK patent material in this product/service is UK Crown copyright 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
Produced by the U.S. National Library of Medicine for database MEDLINE
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
REGISTRY
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 database CASREACT
Copyright 2003 ACS for databases CHEMCATS and CHEMLIST
Bibliographic Information
Deodoring and antiaggregation paste compositions when packaged in pliable bags and containers.
Yoshida, Yasushi; Fujiu, Akira. (Kao Corp., Japan). Jpn. Kokai Tokkyo Koho (2003), 8 pp. CODEN:
JKXXAF JP 2003041483 A2 20030213 Patent written in Japanese. Application: JP 2001-227514
20010727. CAN 138:154400 AN 2003:113002 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 2003041483 A2 20030213 JP 2001-227514 20010727
Priority Application
JP 2001-227514 20010727
Abstract
The title compns. comprise: (A) a polymer contg. units from vinyl acetate and at least one of unsatd. carboxylic
acids or their lower alc. esters, (B) nonionic surfactant, and (C) fragrance substances, and the bags and containers
have all light transmittance at 200-800 nm 30%. Thus, emulsion polymg. cationic-modified starch, with vinyl
acetate, acrylic acid and N,N-dimethylacrylamide gave an A, 65 parts of which was mixed with 3 parts propylene
glycol, 0.2 parts KM 97 (silicone) and C to give a title compn. storaged in a bag laminated from nylon, LDPE and
aluminum foil, wherein C contains: undecyl aldehyde, amyl salicylate, coumarin, cyclamen aldehyde, -ionone,
lavender oil, rose oxide, rosemary oil, and alcs.
Bibliographic Information
Method for polymerizing vinyl monomers and/or oligomers having 1 or more vinyl radicals. Lapairy, Jean-
claude. (Gti Process, Fr.). PCT Int. Appl. (2003), 23 pp. CODEN: PIXXD2 WO 0308463 A1
20030130 Designated States W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR,
CU, CZ, DE, DK, DM, DZ, EC, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR,
KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU,
SD, SE, SG, SI, SK, SL, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZM, ZW, AM, AZ, BY, KG, KZ,
MD, RU, TJ, TM. Designated States RW: AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT,
SE, TR, BF, BJ, CF, CG, CI, CM, GA, ML, MR, NE, SN, TD, TG. Patent written in French. Application: WO
2002-FR2517 20020715. Priority: FR 2001-9636. CAN 138:138869 AN 2003:76826 CAPLUS
(Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
WO 2003008463 A1 20030130 WO 2002-FR2517 20020715
W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN,
CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, ES, FI, GB, GD, GE, GH,
GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS,
LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, OM,
PH, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TN, TR, TT, TZ,
UA, UG, US, UZ, VN, YU, ZA, ZM, ZW, AM, AZ, BY, KG, KZ, MD,
RU, TJ, TM
RW: GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW, AT, BE, BG,
CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL,
PT, SE, SK, TR, BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR,
NE, SN, TD, TG
FR 2827607 A1 20030124 FR 2001-9636 20010717
Priority Application
FR 2001-9636 A 20010717
Abstract
The invention concerns a method for polymg. vinyl monomers and/or oligomers comprising at least a vinyl radical,
which consists in mixing the vinyl monomer or the oligomer comprising at least a vinyl radical with 1 O2-
supplying agent [e.g., Me Et ketone peroxide (I)], 1 aldehyde representing for example between 1% and 15% of the
wt. of the mixt., 1 accelerator which may for example of consist in a metallic salt. A typical compn. for manuf. of
a varnish contained aliph. urethane triacrylate 32, hexanediol diacrylate 23, acidic triacrylate adhesion promoter 7,
Co octoate (6%) 0.3, I (50%) 1, 3,7-dimethyl-2,6-octadienal 5, and hydratropic aldehyde 3.7%.
Bibliographic Information
Perfume encapsulates and their manufacture. Ness, Jeremy Nicholas. (Quest International B.V., Neth.).
PCT Int. Appl. (2002), 13 pp. CODEN: PIXXD2 WO 0274430 A1 20020926 Designated States W:
AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EC,
EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV,
MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TN,
TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZM, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM. Designated States
RW: AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR, BF, BJ, CF, CG, CI, CM,
GA, ML, MR, NE, SN, TD, TG. Patent written in English. Application: WO 2002-GB1133 20020313.
Priority: GB 2001-6560. CAN 137:252689 AN 2002:736169 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
WO 2002074430 A1 20020926 WO 2002-GB1133 20020313
W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN,
CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, ES, FI, GB, GD, GE, GH,
GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS,
LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, OM,
PH, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TN, TR, TT, TZ,
UA, UG, US, UZ, VN, YU, ZA, ZM, ZW, AM, AZ, BY, KG, KZ, MD,
RU, TJ, TM
RW: GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW, AT, BE, CH,
CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR, BF,
BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG
Priority Application
GB 2001-6560 A 20010316
Abstract
The perfume encapsulate comprises an aminoplast capsule, wherein the capsule shell comprising urea-formaldehyde
or melamine-formaldehyde polymer and a second polymer comprising a polymer or copolymer of 1 anhydride,
preferably ethylene-maleic anhydride copolymer. The second polymer improves the stability of the capsules with
respect to surfactant, thus improving perfume retention properties and enabling use of the capsules in aq. surfactant-
contg. products such as shampoo and hair conditions, shower gels, laundry detergent liq., fabric rinse conditioners,
etc. Thus, a perfume encapsulate was manufd. by mixing 60.0 parts perfume contg. allyl amyl glycollate 3.0, citral
di-Et acetal 5.3, linalool 32.0, linalyl acetate 30.2, litsea cubeba oil 3.0 and orange oil Brazilian 26.5% with in an aq.
soln. of urea-formaldehyde or melamine-formaldehyde copolymer and a second polymer comprising anhydride
polymer; and polymg.
Bibliographic Information
Stoichiometric and Catalytic Activation of Si-H Bonds by a Triruthenium Carbonyl Cluster, (3,2:3:5-
acenaphthylene)Ru3(CO)7: Isolation of the Oxidative Adducts, Catalytic Hydrosilylation of Aldehydes,
Ketones, and Acetals, and Catalytic Polymerization of Cyclic Ethers. Nagashima, Hideo; Suzuki, Akihiro;
Iura, Takafumi; Ryu, Kazuhiro; Matsubara, Kouki. Institute of Advanced Material Study Graduate School of
Engineering Science and CREST Japan Science and Technology Corporation (JST), Kyushu University, Kasuga
Fukuoka, Japan. Organometallics (2000), 19(18), 3579-3590. CODEN: ORGND7 ISSN: 0276-7333.
Journal written in English. CAN 133:281909 AN 2000:537651 CAPLUS (Copyright 2003 ACS)
Abstract
Treatment of the Ru cluster (3,2:3:5-acenaphthylene)Ru3(CO)7 (1) with stoichiometric amts. of trialkylsilanes
results in liberation of a CO ligand followed by oxidative addn. of a Si-H bond. The trinuclear silyl complexes
(3,2:3:5-acenaphthylene)Ru3(H)(SiR3)(CO)6 (2) were isolated in good yield. They were characterized by
NMR spectroscopy and x-ray crystallog. Compd. 1 catalyzes the hydrosilylation of olefins, acetylenes, ketones,
and aldehydes. In particular, the reactions of aldehydes and ketones proceed at room temp. to form the
corresponding silyl ethers in good yield; the catalytic activities are superior to those with RhCl(PPh3)3. The
RhCl(PPh3)3-catalyzed hydrosilylation of ketones with Me2(H)SiCH2CH2Si(H)Me2 results in selective reaction of
only one Si-H terminus, while similar reactions, when catalyzed by 1, allow use of both Si-H groups. Significantly
different regio- and stereoselectivities, compared with those obtained in reactions catalyzed by RhCl(PPh3)3, also
were obsd. in the hydrosilylation of ,-unsatd. carbonyl compds. and 4-tert-butylcyclohexanone, resp. The
reactions with acetals and cyclic ethers also take place under similar conditions. The reaction of trialkylsilanes with
an excess of a cyclic ether resulted in ring-opening polymn. Polymn. of THF was studied as a representative
example. Treatment of trialkylsilanes with an excess of THF (10-102 equiv with respect to silanes) in the presence
of a catalytic amt. of 1 gave polytetrahydrofuran with Mn = 1000-200,000 and Mw/Mn = 1.3-2.0. Changing the
ratio of THF to HSiR3 can control the mol. wt. NMR studies suggested that the structure of the polymer is R3SiO-
[(CH2)4O]n-CH2CH2CH2CH3. Mechanistic considerations based on differences in the catalytic activities
between the catalysts 1 and 2 are discussed.
Bibliographic Information
Long-lasting liquid perfume and deodorant compositions. Iida, Yasuo; Hara, Yutaka; Mizuno, Kiyoshi;
Sakaki, Akiko. (Lion Corp., Japan). Jpn. Kokai Tokkyo Koho (2000), 12 pp. CODEN: JKXXAF JP
2000175996 A2 20000627 Patent written in Japanese. Application: JP 98-361192 19981218. CAN
133:63654 AN 2000:427667 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 2000175996 A2 20000627 JP 1998-361192 19981218
Priority Application
JP 1998-361192 19981218
Abstract
The compns., which are placed in containers having wicks at the openings, contain end-capped polyoxyalkylene-
type nonionic surfactants R1CO(AO)m(EO)nOR2 [R1 = (substituted) C6-22 hydrocarbyl; R2 = C1-20 alkyl,
alkenyl; AO = C3-8 oxyalkylene; EO = oxyethylene; m = 0-15; 0 < n 40; m + n = 2-50; the narrow degree of
distribution of EO addn. mol no. is 50 wt.%] or R3CO[(AO)s,(EO)t]OR4 [R3 = same as R1; R4 = same as R2; AO,
EO = same as above; 0 < s 15; 0 < t 40; s + t = 2-50; [(AO)s,(EO)t] indicates random addn. of AO and EO; the
narrow degree of distribution of addn. mol no. of AO and EO is 50 wt.%], perfumes, and H2O. Ethylene oxide
was polymd. in the presence of Me laurate, a fired 2.5MgO.Al2O3 catalyst, and KOH to give polyethylene glycol
laurate Me ether (I) (av. EO addn. mol no. 9.0, narrow degree 70%). A compn. contg. I 3, Na
alkylbenzenesulfonate 1, citrus-type perfumes 2, EtOH 5, Japan Red 106 0.0005, and H2O to 100 wt.% to give a
compn., which showed long-lasting fragrance and did not cause clogging of wicks.
Bibliographic Information
Manufacture of sustained-release microcapsules from polybasic acid halides. Takagi, Emi; Yasue, Ryoji;
Suzuki, Hiroichi; Kiyama, Kentaro. (Lion Corp., Japan). Jpn. Kokai Tokkyo Koho (2000), 5 pp.
CODEN: JKXXAF JP 2000107591 A2 20000418 Patent written in Japanese. Application: JP 98-
277508 19980930. CAN 132:269862 AN 2000:247293 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 2000107591 A2 20000418 JP 1998-277508 19980930
Priority Application
JP 1998-277508 19980930
Abstract
Sustained-release microcapsules, useful for air fresheners, agrochems., insecticides, etc., are manufd. by interfacial
polymn. of polybasic acid halides with compds. having multiple active H atoms in the presence of alk. phosphate
salts. Pore size of microcapsules is controllable by changing method or rate of adding the phosphate salts. An
emulsion contg. PVA (d.p. 500, sapon. degree 88%), terephthaloyl chloride, cis-3-hexenol, C8 aldehyde, C9
aldehyde, C10 aldehyde, citral, linalool, and limonene was treated with an aq. NaOH soln. to form a crosslinked film
and then treated with hexamethylenediamine under portionwise addn. of Na3PO4 at 30 over 5 h to give PVA-nylon
microcapsules with av. particle size 600 m, av. thickness 25.0 m, and av. pore size 7.9 nm. The microcapsules
were shaken in an aq. soln. of a surfactant for 10 h to retain 66% perfumes in the capsules.
Bibliographic Information
Process and apparatus for metering a medium in the gas phase or under supercritical conditions in a pressure
vessel. Hildebrandt, Volker; Breede, Knut; Hlawitschka, Werner. (Basf Aktiengesellschaft, Germany). Eur.
Pat. Appl. (2000), 7 pp. CODEN: EPXXDW EP 978310 A2 20000209 Designated States R: AT, BE,
CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE, SI, LT, LV, FI, RO. Patent written in German.
Application: EP 99-115074 19990805. Priority: DE 98-19835914. CAN 132:153920 AN 2000:98063
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
EP 978310 A2 20000209 EP 1999-115074 19990805
EP 978310 A3 20000830
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT, IE,
SI, LT, LV, FI, RO
DE 19835914 A1 20000217 DE 1998-19835914 19980807
CN 1249207 A 20000405 CN 1999-119514 19990807
Priority Application
DE 1998-19835914 A 19980807
Abstract
A medium in a gas phase or a supercrit. state is charged into a stirring dome of a pressure vessel. The pressure in
the dome is held higher than that in the reaction chamber of the reactor to prevent diffusion of a reaction mixt. from
the reaction chamber to the dome. An app. for charging of the medium into the reactor contains a control valve, a
flowmeter, a pressure buffer, and an optional electronic control unit.
Bibliographic Information
Catalytic processes in industry. Kieboom, A. P. G.; Moulijn, J. A.; Sheldon, R. A.; Van Leeuwen, P. W. N. M.
Gist-brocades BV, Delft, Neth. Studies in Surface Science and Catalysis (1999), 123(Catalysis: An
Integrated Approach (2nd Edition)), 29-80. CODEN: SSCTDM ISSN: 0167-2991. Journal; General Review
written in English. CAN 131:339092 AN 1999:649993 CAPLUS (Copyright 2003 ACS)
Abstract
A review, with several refs. In this chapter a dozen industrial catalytic processes is described, including oil
industry, petrochem. industry, exhaust gas technol., fine chem. industry, polymer prepn., ranging from cracking to
denoxing and asym. catalysis. The descriptions include a brief survey of the chem., the catalyst, the process, and
the reactor. Occasional ref. is made to alternative processes, and the use of the product is briefly indicated.
Bibliographic Information
Flavor enhancement process. Schur, Henry B. (USA). PCT Int. Appl. (1999), 36 pp. CODEN:
PIXXD2 WO 9902046 A1 19990121 Designated States W: AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA,
CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK,
LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM,
TR, TT, UA, UG, US, UZ, VN, YU, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ, TM. Designated States RW: AT, BE,
CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM, GA, ML, MR, NE,
SN, TD, TG. Patent written in English. Application: WO 98-US14116 19980708. Priority: US 97-
889723. CAN 130:138600 AN 1999:70400 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
WO 9902046 A1 19990121 WO 1998-US14116 19980708
W: AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE,
DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP,
KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX,
NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT,
UA, UG, US, UZ, VN, YU, ZW, AM, AZ, BY, KG, KZ, MD, RU, TJ,
TM
RW: GH, GM, KE, LS, MW, SD, SZ, UG, ZW, AT, BE, CH, CY, DE, DK, ES,
FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, BF, BJ, CF, CG, CI, CM,
GA, GN, GW, ML, MR, NE, SN, TD, TG
AU 9886577 A1 19990208 AU 1998-86577 19980708
Priority Application
US 1997-889723 19970708
WO 1998-US14116 19980708
Abstract
The invention relates to the modification of flavorants by reaction of mers in the presence of flavorants to form
products having significantly increased mol. wt.
Bibliographic Information
Water absorption polymer composition and its production method. Nagasuna, Kinya; Motono, Yoshihiro;
Harada, Nobuyuki. (Nippon Shokubai Kagaku Kogyo Co., Ltd., Japan). Jpn. Kokai Tokkyo Koho (1999),
15 pp. CODEN: JKXXAF JP 11005847 A2 19990112 Heisei. Patent written in Japanese.
Application: JP 98-50589 19980303. Priority: JP 97-108823. CAN 130:140061 AN 1999:39920
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 11005847 A2 19990112 JP 1998-50589 19980303
Priority Application
JP 1997-108823 19970425
Abstract
The compn., useful as medical goods and having good release of medicines, comprises a water absorption polymer
and a medicine, wherein the absorption ratio of (absorption ratio before mixing with the medicine at 50 g/cm2)
and absorption ration of (absorption ratio after mixing with the medicine at 50 g/cm2) of the polymer satisfies with
20 g/g, / 0.85. Thus, a compn. having / 0.98, 33 g/g, 26.2 g/g was made from a copolymer, prepd. by
polymg. of Na acrylate and polyethylene glycol diacrylate then crosslinking reaction with ethylene glycol diglycidyl
and propylene glycol, contg. 0.1 % Na Cu chlorophylin.
Bibliographic Information
Electrochemical hydrogenation of citral 5. The use of a nickel electrode in the electrocatalytic process.
Korotayeva, L. M.; Rubinskaya, T. Ya.; Gultyai, V. P. N. D. Zelinsky Institute of Organic Chemistry, Russian
Academy of Sciences, Moscow, Russia. Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk,
Seriya Khimicheskaya) (1998), 47(8), 1487-1490. CODEN: RCBUEY ISSN: 1066-5285. Journal written
in English. CAN 129:295172 AN 1998:596427 CAPLUS (Copyright 2003 ACS)
Abstract
The conditions for preparative electrocatalytic hydrogenation of citral to citronellol were found. Changes in the
electrocatalytic properties of the nickel cathode depend on the method of pretreatment of the electrode (mech.
surface cleaning, thermal treatment, cathode-anode activation, and electrodeposition). The use of the nickel
cathode with the surface covered with dispersed nickel in electrocatalytic hydrogenation was recommended.
Bibliographic Information
Preparation of citral acetal ethers of -hydroxy phenyl ketones and photopolymerizable coating
compositions. Share, Paul E. (Henkel Corp., USA). PCT Int. Appl. (1994), 30 pp. CODEN:
PIXXD2 WO 9429355 A1 19941222 Designated States W: AU, BR, CA, CN, JP, KR, NZ. Designated
States RW: AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE. Patent written in English.
Application: WO 94-US5583 19940524. Priority: US 93-73007. CAN 123:202325 AN 1995:806282
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
WO 9429355 A1 19941222 WO 1994-US5583 19940524
W: AU, BR, CA, CN, JP, KR, NZ
RW: AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE
AU 9469163 A1 19950103 AU 1994-69163 19940524
US 5466721 A 19951114 US 1994-258917 19940613
Priority Application
US 1993-73007 19930604
WO 1994-US5583 19940524
Abstract
The title compds. [I; R1, R2 = H, (hetero)alkyl, aryl, heterocyclyl; R1R2 may form a divalent (hetero)aliph. radical;
R3, R4 = (hetero)alkyl, aryl, heterocyclyl; n = 0-5] are useful as both monomers and photoinitiators in radiation-
curable compns. Thus, a 96:4 (wt. parts) blend of Photomer 3015 (II) with benzoin Me citral acetal (prepn. by
transacetalization of citral di-Me acetal with benzoin given) was coated on Al panels and cured at conveyor belt
speed of 100 ft/min using a 300 W/in Hg bulb to give 6.86-m-thick coating having pencil hardness 4H and 22-26
MEK rubs, vs. 3H and 17-88 for a 96:4 II-Irgacure 651 blend.
Me R1 O
Me (R 3 ) n
Me O
OR 4 R2
I
Bibliographic Information
Aromatization of hydrocarbons by the "Cp*Ru+" fragment: reactions with terpenes and cyclizations.
Carreno, R.; Urbanos, F.; Dahan, F.; Chaudret, B. Lab. Chim. Coordinat., Univ. Paul Sabatier, Toulouse, Fr.
New Journal of Chemistry (1994), 18(4), 449-55. CODEN: NJCHE5 ISSN: 1144-0546. Journal written in
English. CAN 121:134443 AN 1994:534443 CAPLUS (Copyright 2003 ACS)
Abstract
The "Cp*Ru+" (1) fragment reacts with carvone to give the carvacrol complex [Cp*Ru(6-C10H13OH)](CF3SO3)
(2; shown as I) through isomerization and with carvyl acetate to give the p-cymene complex, [Cp*Ru(6-C10H14)]
(CF3SO3) (3), through elimination of acetic acid. The structure of 2 was detd. by x-ray crystallog. The reactions
with carene, verbenone and camphor which contain, resp., C3, C4 and C5 strained rings yield, resp., [Cp*Ru(4-
C10H14)](CF3SO3) (4) formed upon dehydrogenation of carene into the diene analog, an intractable mixt., and a
mixt. of aromatized product including [Cp*Ru(6-C6H5CH3)](CF3SO3) as the major component. Reactions of 1
with hexatriene, hexadienal and hexadienol yield [Cp*Ru(6-C6H6)](CF3SO3) and, resp., H2, H2O and H2/H2O.
The reaction is selective in the first two cases, accompanied by polymn. in the third one. Finally, citral reacts with
1 to give the p-cymene complex 3 and H2O.
Me Me
Me
+
Me Ru CF 3 SO 3 -
Me CHMe 2
Me I
Bibliographic Information
Slowly evaporating terpenoid-containing composition for air treatment. Sato, Shoichi; Tabuchi, Toshi;
Urushida, Shigeo; Shimizu, Sakae. (Ricoh Co., Ltd., Japan). Ger. Offen. (1994), 10 pp. CODEN:
GWXXBX DE 4340609 A1 19940623 Patent written in German. Application: DE 93-4340609
19931129. Priority: JP 92-345425. CAN 121:117399 AN 1994:517399 CAPLUS (Copyright 2003
ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
DE 4340609 A1 19940623 DE 1993-4340609 19931129
DE 4340609 C2 19941124
JP 06157352 A2 19940603 JP 1992-345425 19921130
JP 3255191 B2 20020212
US 5567416 A 19961022 US 1993-158399 19931129
Priority Application
JP 1992-345425 A 19921130
Abstract
A slowly evapg. compn. contg. a terpenoid as active agent and an antioxidant absorbed in an oil-absorbing
polymeric network, optionally together with a noncombustible org. material, is useful for disinfecting and
deodorizing the air, decompg. O3, and as an insecticide. Thus, a mixt. of gelatin 0.5, tert-Bu methacrylate 50,
divinylbenzene 0.025, and Bz2O2 0.25 g in H2O was polymd. at 80, and the polymer was shaped into an oil-
absorbing plate which was soaked in a mixt. of d-limonene 59.2, fluorocarbon HCFC-225 45.8, and BHT 5 g. This
plate lost 1.16 g limonene/day by evapn., lost no limonene by sweating, and decreased the O3 concn. in air in a
desiccator test by 95% in 1 h.
Bibliographic Information
Electrocatalytic hydrogenation of organic compounds on carbon electrodes modified by poly(pyrrolebis[2,2'-
bipyridyl] palladium(II) complex) films. Deronzier, A.; Moutet, J. C.; Saint-Aman, E. Lab. Electrochim.
Org. Photochim. Redox, Univ. Joseph Fourier Grenoble 1, Grenoble, Fr. Journal of Electroanalytical
Chemistry (1992), 327(1-2), 147-58. CODEN: JECHES Journal written in English. CAN 117:120338
AN 1992:520338 CAPLUS (Copyright 2003 ACS)
Abstract
The electrochem. behavior of the bis[2,2'-bipyridyl] palladium(II) complex in CH3CN is described. The redn. of
this complex is characterized by a one-electron transfer followed by a reversible chem. step and a second
irreversible one-electron transfer. Carbon felt electrodes have been modified by electropolymn. of a pyrrole-
substituted bis[2,2'-bipyridyl] palladium(II) complex giving a mol. electrode material useful for electrocatalytic
hydrogenation of org. compds. On these cathodes, the activated carbon-carbon double bond of a series of enones
are hydrogenated in preference to the carbonyl group. The influence of the complex loadings and the initial amt. of
substrate has also been investigated.
Bibliographic Information
Naphthalenemethanol derivatives, a method for their preparation and perfume compositions containing
them. Giersch, Wolfgang Klaus; Ohloff, Guenther. (Firmenich S. A., Switz.). Eur. Pat. Appl. (1988),
6 pp. CODEN: EPXXDW EP 282798 A2 19880921 Designated States R: CH, DE, FR, GB, LI, NL.
Patent written in French. Application: EP 88-102990 19880229. Priority: CH 87-1006. CAN 111:45073
AN 1989:445073 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
EP 282798 A2 19880921 EP 1988-102990 19880229
EP 282798 A3 19900613
EP 282798 B1 19920909
R: CH, DE, FR, GB, LI, NL
JP 63253039 A2 19881020 JP 1988-62078 19880317
US 4818747 A 19890404 US 1988-169536 19880317
Priority Application
CH 1987-1006 19870317
Abstract
Bicyclic aliph. alcs. (I; substituents are both attached at C-2 or C-3) are used as fragrance in perfume compns. I are
prepd. by a reaction of myrcene with Et methacrylate in a Diels-Alder reaction, followed by cyclization in the
presence of an acidic catalyst, catalytic hydrogenation, and redn. of the ester thus obtained to give I as an isomeric
mixt. This mixt. can be used directly or isomers can be sepd. by gas chromatog. I has a natural wood note,
resembling cedar wood with an amber subnote; this amber note offset aspects evoked by ambergris or e.g. Ambrox.
I has a sweet note that harmonizes with the amber note. A mixt. contg. myrcene 72, Et methacrylate 66,
cyclohexane 100, and hydroquinone 0.2 (polymn. inhibitor) was heated in an autoclave at 160 for 24 h. The
product mixt. was cooled, treated with 10 mL BF3-Et2O and allowed to stand for 24 h to give 65% Et
1,2,3,4,5,6,7,8-octahydro-2,5,5(2,8,8)-trimethyl-2-naphthalenecarboxylate. The latter (933 g) was catalytically
hydrogenated in the presence of 2 g Raney Ni to give 98% Et perhydro-2,5,5(2,8,8)-trimethyl-2-
naphthalenecarboxylate, which (920 g) was hydrolyzed in the presence of 1850 mL 25% Na diethylaluminate to
give 712 g I. A men's cologne contained AcOCH2Ph 200, cinnamyl alc. 50, hexylcinnamic aldehyde 300, basil
essence 50, natural bergamot essence 3500, citral 1000, clove essence 400, synthetic geranium essence 100,
lavender essence 1500, methylionone 600, Me dihydrojasmonate 1000, Neroli Bigarde 150, heliopropanal 150,
Bourbon vetiver 100 parts by wt.
Me Me
CH 2 OH
Me
H I
Bibliographic Information
Resin compositions for electrophotographic toner. Matsunaga, Takayoshi; Tanaka, Susumu; Watanabe,
Hisashi. (Sekisui Chemical Co., Ltd., Japan). Jpn. Kokai Tokkyo Koho (1987), 9 pp. CODEN:
JKXXAF JP 62156668 A2 19870711 Showa. Patent written in Japanese. Application: JP 85-298721
19851227. CAN 109:46110 AN 1988:446110 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 62156668 A2 19870711 JP 1985-298721 19851227
JP 06095227 B4 19941124
Priority Application
JP 1985-298721 19851227
Abstract
The title compns. for color toners contain plant essential oils, and a copolymer of (meth)acrylic tertiary amine,
styrene deriv. (meth)acrylic ester, and monomers having carboxy groups. The compns. have strong pos.
chargeability, have no smell of maines, and do not discolor on use. Thus, styrene 850, n-Bu acrylate 92.5,
dimethylaminoethyl acrylate 37.5, and monoacryloyloxyethyl hydrogen succinate 20 g were polymd. in PhMe,
added with 0.5 g essential oil (contg. 1 of camphor, limonene, citral, geraniol, cineole, -terpineol, and 3-carene),
and ripened. The oil-added copolymer was colorless, and no scale was found on the vessel wall. An
electrophotog. developer using the toner from the resin and Fe carrier showed +17 C/g charge capacity, and had no
smell. A control resin prepd. not using the succinate ester and essential oil was colored brown, and had amine odor.
Bibliographic Information
Laser-induced damage study of polycitral films. Augustine, M. Sajimol; Radhakrishnan, P.; Jayalakshmi, S.;
Pillai, M. G. Krishna. Dep. Phys., Cochin Univ. Sci. Technol., Cochin, India. Bulletin of
Electrochemistry (1988), 4(2), 177-8. CODEN: BUELE6 ISSN: 0256-1654. Journal written in English.
CAN 109:7640 AN 1988:407640 CAPLUS (Copyright 2003 ACS)
Abstract
Laser-induced damage threshold of polycitral films was measured using a dye Q-switched Nd glass laser emitting
25-ns pulses at 1062 nm. It showed neither the behavior exhibited by conventional dielec. films nor that by
polymer films. However, the present observations established the good optical characteristics of these films with a
high damage threshold and their usefulness as optical coatings in laser systems.
Bibliographic Information
Compositions forming nascent organic peroxides and their use. Chevrier, Andre. (Fr.). Fr. Demande
(1987), 8 pp. CODEN: FRXXBL FR 2599042 A1 19871127 Patent written in French.
Application: FR 86-7844 19860523. CAN 108:113648 AN 1988:113648 CAPLUS (Copyright 2003
ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
FR 2599042 A1 19871127 FR 1986-7844 19860523
FR 2599042 B1 19890616
Priority Application
FR 1986-7844 19860523
Abstract
The title compns. are prepd. by mixing high-mol. wt. unsatd. polyoxyethylenes with reducing agents (e.g.
autoxidizable aldehydes, unsatd. phenols) and treating the mixt. with O or air at 55. Exposing a mixt. of BzH 1,
triethylene glycol 3, and polyethylene glycol ester with castor oil 2 parts and a disinfectant to air, optionally in the
presence of H2O, gave a compn. which could be used as a disinfectant, bactericide, or deodorant.
Bibliographic Information
Organosilanol compositions. Noda, Seiji; Yasumasu, Tomoko. (Lion Corp., Japan). Jpn. Kokai Tokkyo
Koho (1986), 5 pp. CODEN: JKXXAF JP 61129185 A2 19860617 Showa. Patent written in
Japanese. Application: JP 84-251248 19841128. CAN 106:67477 AN 1987:67477 CAPLUS
(Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 61129185 A2 19860617 JP 1984-251248 19841128
JP 05005835 B4 19930125
Priority Application
JP 1984-251248 19841128
Abstract
RnSi(OH)4-n compns. (R = C1-6 alkyl, alkenyl, alkoxy, cycloalkyl, etc., n = 0-3) are stabilized with C6-17
aldehyde, ester, ketone, and/or C7-17 arom. acid. The compns. are useful as cosmetic lotions. Thus, an aq. soln.
of MeSi(ONa)3 was neutralized with H-type cation-exchanger resins at pH 6.5 and treated with PhCO2Me to give a
soln. of 1% MeSi(OH)3 and 1% PhCO2Me of pH 6.5, which stayed clear after 2 wk, vs. a cloudy soln. resulting
from silanol polymn. after 1 day without PhCO2Me.
Bibliographic Information
Unsaturated acetals as citral precursors. Ninagawa, Yoichi; Kyo, Sunao. (Kuraray Co., Ltd., Japan). Jpn.
Kokai Tokkyo Koho (1986), 4 pp. CODEN: JKXXAF JP 61022037 A2 19860130 Showa. Patent
written in Japanese. Application: JP 84-141073 19840706. CAN 105:134189 AN 1986:534189
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 61022037 A2 19860130 JP 1984-141073 19840706
JP 64000377 B4 19890106
Priority Application
JP 1984-141073 19840706
Abstract
Me2C:CHCH(OCH2CH:CMe2)2 (I) was prepd. by heating Me2C:CHCHO (II) and Me2C:CHCH2OH (III) at 40-
110 using MgSO4 as an acid catalyst. Thus, a mixt. of II, III, and anhyd. MgSO4 was heated at 80-82 and 70-60
torr for 7 h, while H2O was removed as an azeotrope with II and III, to give 96.8% I (based upon II). I is useful as
a precursor for the synthesis of citral and diisoamyl ether, a catalyst modifier for olefin polymn.
Bibliographic Information
Unsaturated acetals as citral precursors. Ninagawa, Yoichi; Kyo, Sunao. (Kuraray Co., Ltd., Japan). Jpn.
Kokai Tokkyo Koho (1986), 5 pp. CODEN: JKXXAF JP 61022038 A2 19860130 Showa. Patent
written in Japanese. Application: JP 84-141074 19840706. CAN 105:134188 AN 1986:534188
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 61022038 A2 19860130 JP 1984-141074 19840706
JP 64000378 B4 19890106
Priority Application
JP 1984-141074 19840706
Abstract
Me2C:CHCH(OCH2CH:CMe2)2 (I) was prepd. by heating Me2C:CHCHO (II) and Me2C:CHCH2OH (III) at
below 65 in the presence of NiSO4, CoSO4 or (NH4)2SO4. Thus, a mixt. of II, III, and NiSO4.6H2O in heptane
was heated at 50-54 and 135 torr, while H2O was removed as an azeotrope with the solvent, to give 69.0% I (based
upon II). I is useful as an intermediate for the synthesis of citral and diisoamyl ether, a catalyst modifier for olefin
polymn.
Bibliographic Information
Photopolymerizable composition. Hino, Kenichi; Yamauchi, Junichi; Nishida, Koji. (Kuraray Co., Ltd.,
Japan). Eur. Pat. Appl. (1985), 41 pp. CODEN: EPXXDW EP 150952 A2 19850807 Designated
States R: DE, FR, GB, IT, NL. Patent written in English. Application: EP 85-300264 19850115. Priority:
JP 84-6797. CAN 103:220855 AN 1985:620855 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
EP 150952 A2 19850807 EP 1985-300264 19850115
EP 150952 A3 19850821
EP 150952 B1 19890830
R: DE, FR, GB, IT, NL
JP 60149603 A2 19850807 JP 1984-6797 19840117
JP 04019245 B4 19920330
US 4668712 A 19870526 US 1985-689302 19850107
Priority Application
JP 1984-6797 19840117
Abstract
A photopolymerizable compn. for dental uses comprises a polymerizable monomer such as a methacrylate ester and
an initiator capable of polymg. the monomer upon exposure to visible light and which cures at a high rate to a
sufficient depth, that hardly discolors and has good stability. The initiator consists of at least 1 photosensitizer such
as a diketone A(CO)2A (A = C1-20 aliph. hydrocarbon or A2 = cyclic structure) and quinone I-VI (A' = C1-20 aliph.
hydrocarbon or 2-4 H), at least 1 accelerator such as an aldehyde B(CHO)n (B = C1-20 (un)satd. aliph. or arom.
hydrocarbon; n = 1-3), and an org. peroxide. thus, a monomer liq. was prepd. from bis-GMA-triethyleneglycol
dimethacrylate-neopentylglycol copolymer [99294-07-2] (70, 15, and 15 parts by wt., resp.) 239.8, and to this were
added 1 wt.% camphorquinone [465-29-2], p-tolualdehyde [104-87-0] 4.5, and Bz2O2 [94-36-0] 2.3 mg. The
compn. irradiated with visible light has a curing time of 30 s compared to 47 s for control.
O
O O O
O
A'
O
A' A' I A' A' II A' II I
O O O
A' A'
A' A' A'
O IV O V O VI
Bibliographic Information
Preparation and characterization of a new high quality polymer thin film from citral. Jayalekshmi, S.;
Pillai, M. G. Krishna. Dep. Phys., Univ. Cochin, Cochin, India. Thin Solid Films (1984), 122(3),
197-202. CODEN: THSFAP ISSN: 0040-6090. Journal written in English. CAN 103:15412 AN
1985:415412 CAPLUS (Copyright 2003 ACS)
Abstract
A new high-quality polymer film with excellent dielec. properties was obtained by polymg. citral in a radio-
frequency glow discharge. The variations in the dielec. const. and the loss factor for Al/polycitral/Al sandwich
structures were studied over the frequency range from 500 Hz to 25 kHz, at 303-573 K. The current-voltage
characteristics were studied from zero to 1000 V. From IR studies a possible mechanism of polymn. is suggested.
Bibliographic Information
Sustained-release fragrant compositions. (Asahi Glass Co., Ltd., Japan; Takasago Perfumery Co., Ltd.).
Jpn. Kokai Tokkyo Koho (1984), 7 pp. CODEN: JKXXAF JP 59155451 A2 19840904 Showa.
Patent written in Japanese. Application: JP 83-27036 19830222. CAN 102:67239 AN 1985:67239
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
JP 59155451 A2 19840904 JP 1983-27036 19830222
JP 63028458 B4 19880608
US 4582635 A 19860415 US 1984-579582 19840213
GB 2138006 A1 19841017 GB 1984-4098 19840216
GB 2138006 B2 19860409
Priority Application
JP 1983-27036 19830222
Abstract
Sustained-released fragrant compns. are prepd. by polymg. diethylene glycol bis(allyl carbonate) in the presence of
perfumes. The compns. may be applied to air fresheners, decorative accessories, furniture, etc. Thus, a mixt. of
diethylene glycol bis(allylcarbonate), diisopropyl peroxydicarbonate (a polymn. initiator), and octyl alc. [111-87-5]
was heated up to 45.apprx.50 for 5 h, cooled slowly in 2 h to 90, and reheated to 90.apprx.95 for 11 h to obtain a
fragrant compn. which may be used as an air freshener. The effect of the polymer on odor and stability of a no. of
fragrant compds. was given.
Bibliographic Information
Solubility of polystyrene in certain vegetable oils, essential oils and their constituents. Monte, Woodrow C.;
Landau-West, Debra. Dep. Home Econ., Arizona State Univ., Tempe, AZ, USA. Journal of Food
Science (1982), 47(6), 1832-5. CODEN: JFDSAZ ISSN: 0022-1147. Journal written in English. CAN
98:33227 AN 1983:33227 CAPLUS (Copyright 2003 ACS)
Abstract
Certain food items have been shown to be incompatible with the expanded polystyrene [9003-53-6] used for the
manuf. of food containers. Using 14C polystyrene (synthesized in such a way as to approx. the structure of com.
polystyrene), it was detd. that this incompatibility was due, in part, to the dissocn. of polystyrene by certain essential
oils. Citronella, limonene-D [5989-27-5], and terpinene [8013-00-1] (constituents of many flavor oils) were
excellent solvents for polystyrene, solubilizing almost 0.5 g/g of solvent at room temp.
Bibliographic Information
Mixing flavors and fixed composition comprising derivatized synthetic polysaccharides. Furda, Ivan;
Malizia, Peter D. (General Foods Corp., USA). U.S. (1976), 4 pp. CODEN: USXXAM US 3973049
19760803 Patent written in English. Application: US 74-450944 19740314. CAN 85:122122 AN
1976:522122 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
US 3973049 A 19760803 US 1974-450944 19740314
CA 1041490 A1 19781031 CA 1975-219714 19750210
Priority Application
US 1974-450944 19740314
Abstract
Water-insol. flavors may be fixed and stabilized to oxidn. by mixing with an acid-polymd. synthetic polysaccharide
esterified with a substituted dicarboxylic acid anhydride. Thus, 120 g 1-decenylsuccinylated polyglucose (I) [2519-
16-6], prepd. by alk. esterification of polyglucose [25191-16-6] with 1-decenylsuccinic anhydride, was dissolved in
360 ml H2O and blended with 30 g model citrus essential oil (Et butyrate-limonene-linalool-citral, 1:1:1:1 by wt.)
for 45 min. The emulsion was freeze-dried and stored 6 weeks at 85% relative humidity and 90F in a glassine
pouch. Retention of the model oil was much better with I than with gum arabic or starch derivs. Polyglucose
prepd. by polymn. in the presence of citric acid was superior to that prepd. in the presence of H3PO4 or HCl.
Bibliographic Information
Di- and tetra-(peroxy)ketals and acetals and improved curing and polymerizing process employing same.
Sanchez, Jose. (Pennwalt Corp., USA). U.S. (1976), 10 pp. CODEN: USXXAM US 3950432
19760413 Patent written in English. Application: US 72-242821 19720410. CAN 85:47505 AN
1976:447505 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
US 3950432 A 19760413 US 1972-242821 19720410
JP 49017879 A2 19740216 JP 1973-18482 19730216
JP 56029681 B4 19810710
DE 2317965 A1 19731025 DE 1973-2317965 19730410
DE 2317965 C2 19820819
Priority Application
US 1972-242821 19720410
Abstract
The condensation of aldehydes or ketones with Me3CCH2CMe2OOH in pentane contg. H2SO4 gave a series of 20
gem-bis(1,1,3,3-tetramethylbutylperoxy)alkanes (I) which could be used as catalysts for polymn. or crosslinking.
For example, At 5 10-4 initiator equiv. concn. the relative polymn. rates of styrene initiated with 4-methyl-2,2-
bis(1,1,3,3-tetramethylbutylperoxy)pentane [51319-25-6] and BzOOCMe3 (std. initiator) were in 2.17:1 ratio.
Similarly, the cure times of an alkyd resin with 2,2-bis(1,1,3,3-tetramethylbutylperoxy)butane [50602-72-7] and
BzOOCMe3 were 5.3 and 14.3 min resp.
Bibliographic Information
Autoxidation of some constituents of hops. I. Monoterpene hydrocarbon, myrcene. Dieckmann, Robert
H.; Palamand, S. Rao. Tech. Cent., Anheuser-Busch, Inc., St. Louis, MO, USA. Journal of Agricultural
and Food Chemistry (1974), 22(3), 498-503. CODEN: JAFCAU ISSN: 0021-8561. Journal written in
English. CAN 81:62081 AN 1974:462081 CAPLUS (Copyright 2003 ACS)
Abstract
Controlled degrdn. of myrcene, the major monoterpene hydrocarbonof hop oil, is discussed, with special emphasis
on the role of myrcene as a precursor for the formation of flavor compds. occurring in naturally aging hop oil.
Products were isolated and identified by means of gas chromatog., mass spectral, and ir analyses. Related possible
degrdn. pathways were suggested for a no. of these 2nd- and 3rd-order terpenoid constituents, and spectral data for
several terpene alcs., oxides, ketones, and polymn. products were reported.
Bibliographic Information
Electrochemistry of - unsaturated aldehydes. Vadaszy, Richard; Cover, Richard E. Dep. Chem., St.
John's Univ., Jamica, NY, USA. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry
(1974), 49(3), 433-41. CODEN: JEIEBC ISSN: 0022-0728. Journal written in English. CAN 80:103179
AN 1974:103179 CAPLUS (Copyright 2003 ACS)
Abstract
The electrochem. behavior of 9- unsatd. aldehydes was investigated by d.c. polarog., a vibrating-dropping Hg
electrode, controlled-potential electrolysis, and cyclic voltammetry. Compds. having alkyl substituents exhibited a
single polarog. wave. Acrolein and sorbaldehyde had multiple waves, the most pos. of which, like the waves of the
alkyl compds., resulted from redn. via a 1-electron 1-proton process. The 2nd waves of acrolein and sorbaldehyde
came from the 1-electron redn. of the product formed by hydration of the - double bond. Electrolysis products
of several compds. were isolated and examd. by ir and mass spectroscopy and by gas and thin-layer
chromatography. The free radicals formed by these electrochem. processes initiated head-to-tail polymerization of
the aldehydes.
Bibliographic Information
Di(tert-octylperoxy)alkane crosslinking and polymerization catalysts. Sanchez, Jose. (Pennwalt Corp.).
Ger. Offen. (1973), 32 pp. CODEN: GWXXBX DE 2317965 19731025 Patent written in German.
Application: DE 73-2317965 19730410. CAN 80:37638 AN 1974:37638 CAPLUS (Copyright 2003
ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
DE 2317965 A1 19731025 DE 1973-2317965 19730410
DE 2317965 C2 19820819
US 3950432 A 19760413 US 1972-242821 19720410
Priority Application
US 1972-242821 19720410
Abstract
RCMe(OOCMe2CH2CMe3)2 (R = Me, Et, CH2, CHMe2, Bu) were prepd. and used for crosslinking alkyd resins
and as polymn. catalysts for styrene. Thus, H2SO4 was added to MeCOEt and Me3CCH2CHMe2OOH in pentane
and the mixt. stirred 4 hr at 0.deg. to give 59.5% 2,2-di(tert-octylperoxy)butane (I) [50602-72-7]. A resin of
viscosity (Brookfield no. 2 at 20 rpm) 13.08 P and sp.gr. 1.14, by addn. of 3 parts styrene [100-42-5] to 7 parts
1.0:1.0:2.2 moles maleic anhydride-phthalic anhydride-propylene glycol copolymer [25037-66-5] of acid no. 45-50,
was crosslinked in the presence of I according to SPI procedure for running exotherm curves at gelation time 3.9
min and crosslinking time 5.3 min vs. 11.8 and 14.3 min, resp., for the same procedure in the presence of tert-Bu
peroxybenzoate. Also prepd. were 16 other di(tert-octylperoxy)alkanes.
Bibliographic Information
Radiolysis of aldehydes. Wheeler, Owen H.; Diaz de Osborne, Elba. Puerto Rico Nucl. Center, Mayaguez,
P. R. International Journal of Applied Radiation and Isotopes (1969), 20(7), 549-51. CODEN: IJARAY
ISSN: 0020-708X. Journal written in English. CAN 71:65991 AN 1969:465991 CAPLUS
(Copyright 2003 ACS)
Abstract
The effect of 60Co -radiation on decanal, citral, citronellal, and Ph-CHO was detd. The dose in megarads and G-
M are, resp., 4.1, 62.0; 4.6-13.6, 19.6 3.4; 7.5, 21.7 0.2; 5.3, 66.8 0.6. No gaseous products were detected in
the radiolyzed samples. No citronellol was detected in the radiolysis of citronellal and no cyclocitral was found in
the citral. The G-M values for 0.1-0.2% solns. in oxygenated 0.8N HOAc soln. were 4.8 for citral and 6.5 for
citronellal, both at 4.7-5.3 megarads. Considerable amts. of org. peroxide (G .apprx. 10) were found in the
radiolyzed solns.; no other org. material was extd. with CHCl3. The smaller G-M values for the unsatd. aldehydes
suggest that the energy distributed along the chain can be dissipated through the double bonds. Citral and
citronellal in aq. HOAc were attacked readily by radicals formed from water. The aldehydes in essential oils are
polymd. by radiolysis which should not alter the flavor value of these oils.
Bibliographic Information
Effect of -irradiation on lemon oil and lemon-grass oil. Wheeler, Owen H.; Diaz de Osborne, Elba.
Puerto Rico Nucl. Center, Mayaguez, P. R. Journal of Agriculture of the University of Puerto Rico (1969),
53(1), 75-6. CODEN: JAUPA8 ISSN: 0041-994X. Journal written in English. CAN 70:66869 AN
1969:66869 CAPLUS (Copyright 2003 ACS)
Abstract
To det. the effect of -radiation on the flavor of foods, citral and citronellal (major constituents of lemon oils) were
irradiated. Although they both undergo radiolytic decompn. only nonvolatile polymers, which do not affect the
flavor, are formed.
Bibliographic Information
Terpenoids. CXVI. Evaluation of po,yesters as stationary phases in gas-liquid chromatography of
terpenoids. Bapat, B. V.; Sankpal, T. K.; Ghatge, Bhaushe B.; Bhattacharyya, Sasanka C. Natl. Chem. Lab.,
Poona, India. Journal of Chromatography (1967), 29(2), 333-40. CODEN: JOCRAM ISSN: 0021-9673.
Journal written in English. CAN 68:65534 AN 1968:65534 CAPLUS (Copyright 2003 ACS)
Abstract
Polyesters obtained by the self-polymn. of aleuritic acid (I) and -hydroxystearic acid (II) were evaluated as
stationary phases in the gas-liq. chromatog. of terpenoids. The acids were polymd. by heating 2.425 g. I or 2.435 g.
II on the column filling (with a fire-brick support) for 6 hrs. with const. stirring. Losses during the heating were
0.381 g. I and 0.219 g. II. Retention time data are tabulated for various terpenoids on the I and II polyester
columns. The acid-catalyzed decompn. of tertiary alcs. on the polyester columns is retarded by making the
columns slightly alk. by treatment with KOH in aq. alc. The polyester columns exhibit high solubilities for
nonpolar sesquiterpenic hydrocarbons and can be used to sep. them from monoterpenic oxygenated compds. The
retention data for the I and II polyester columns are compared with those for polyesters prepd. from adipic acid and
1,4-butanediol or 1,4-butenediol, pentadecane-1,15-dicarboxylic acid-diethylene glycol polyester, and Apiezon.
Bibliographic Information
Modifying cellulosic materials with ionizing radiation. Munzel, Fritz. (Heberlein & Co. A.-G.). (1966),
7 pp. US 3254939 19660607 Patent language unavailable. Application: US 19600517. CAN 65:39201
AN 1966:439201 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
US 3254939 19660607 US 19600517
Abstract
The properties of cellulose and regenerated cellulose textiles (I) are improved by treating I with ionizing radiation of
a critical dose between 103 and 107 rads in the presence of a radiation sensitizer (II) and a graftable org. finishing
agent which is applied to I and grafted to it. II is applied to I from a dil. aq. media. Graftable polymerizable
polymers such as vinyl or allyl compds. or ethylene-type unsatd. monomers may be used for grafting as well as
polymers. Thus, a cotton poplin fabric was treated at 20 in a H2O bath contg. 1 wt. % 1,4-diphenylbenzene and
dried at 60-70. It was then irradiated at an ambient moisture content of 8% to a total dose of 105 rads from a 60Co
source. The resulting fabric was insol. in cuprammonium soln.
Bibliographic Information
Physical properties and kinetics of certain reactions of the isomers of alloocimene. Cappas, Constantine.
Univ. of Florida, Gainesville, Avail. Univ. Microfilms (Ann Arbor, Mich.), Order No. 62-3930. (1962),
162 pp. From: Dissertation Abstr. 23,846. Dissertation language unavailable. CAN 58:14987 AN
1963:14987 CAPLUS (Copyright 2003 ACS)
Bibliographic Information
Essential oils. X. Elsholtzia ketone and naginata ketone, the main constituents of a new Perilla oil. Yeh,
Ping-Hsien. Prov. Ind. Research Inst., Taipei, Formosa, Journal of the Chinese Chemical Society (Taipei,
Taiwan) (1961), 8 114-25. CODEN: JCCTAC ISSN: 0009-4536. Journal language unavailable. CAN
56:53862 AN 1962:53862 CAPLUS (Copyright 2003 ACS)
Abstract
cf. ibid. 6, 127(1960); CA 49, 11964a. A new species of Perilla which is morphologically indistinguishable from P.
frutescens var. crispa f. viridis was found in Taiwan and named P. naginataketoniferum. On steam distn. it gave
0.4% essential oil, the constituents of which were ( - )-limonene 2.4, elsholtzia ketone (I) 48.0, naginata ketone (II)
36.7, -caryophyllene 8.6%, and small amts. of dipentene and acids. Since catalytic hydrogenation of II gave I, II
is 1-(-methyl--furoyl)2-methyl-1-propene. The taxonomic relations between various spp. of Perilla were
discussed from the possible routes by which the biosynthesis of the main constituents in the oil might be brought
about in Perilla spp., that is: (a) geraniol citral neral II I; (b) citral perillene perilla ketone; (c)
geraniol nerol -terpineol limonene perillaldehyde; and (d) nerol piperitol piperitone. P. citriodora
which contains 59% citral and a small amt. of perillone in its essential oil may be regarded taxonomically as a parent
plant of Perilla spp. Infrared spectra of I, II, I 2,4-dinitrophenylhydrazone, and dihydronaginata ketone 2,4-
dinitrophenylhydrazone, and II 2,4-dinitrophenylhydrazone are given.
Bibliographic Information
Infrared spectra and structure of telomerization of diene hydrocarbons with halogen derivatives. Petrov,
A. A.; Yakovleva, T. V. Izvestiya Akademii Nauk SSSR, Seriya Fizicheskaya (1959), 23 1217-18. CODEN:
IANFAY ISSN: 0367-6765. Journal language unavailable. CAN 54:32617 AN 1960:32617 CAPLUS
(Copyright 2003 ACS)
Abstract
In the reaction of diene hydrocarbons with halogen derivs. in the presence of Sn, Ti, Zn, or Fe chloride to form
telomers of the compn. R(CnH2n-2)xCl, 1,2 and 1,4 products are formed, the structure of which can best be detd.
from their infrared spectra. Such structures can be derived from frequencies 1635, 1660, and 1680 cm.-1,
corresponding to valence vibrations of groups CH:CH2, CH:CH, and C:CH2; the presence of deformation bands;
and the presence of the band for :C-H at 3030 cm.-1 and its harmonic at 6100 cm.-1 In the telomerization of 2-
chloro-3-pentene with isoprene, piperylene, and chloroprene, 1,4 products are formed to 85-90%; the bands of
CH:CH are strong, and the vinyl bands are absent. Infrared spectra permitted analysis of the mixt. obtained from
the reaction of isoprene with its hydrochloride to geranyl, linalyl, and terpenyl chloride. Spectroscopic analysis
also indicated that the synthetic citral is not identical with the natural product.
Bibliographic Information
Conformational effects and the influence of pressure on reaction rates. Whalley, E. Natl. Research
Council, Ottawa, Canadian Journal of Chemistry (1958), 36 228-37. CODEN: CJCHAG ISSN: 0008-
4042. Journal language unavailable. CAN 52:54097 AN 1958:54097 CAPLUS (Copyright 2003
ACS)
Abstract
It has been suggested that the pressure coeff. of the rate consts. of some reactions may be influenced by the
formation of inter or intramol. conformations prior to reaction. This is examd. theoretically, and the relevant exptl.
evidence is discussed. No examples of an effect in which the conformations are at equil. are known with certainty,
but the effect of pressure on termination in the polymerization of styrene appears to be an example of such an effect
when the conformations are not at equil. The pressure coeff. of the rate const. for the isomerization of citraldehyde
to 3,8-carvomenthenediol is not consistent with a unimol. slow step (Price and Dickman, C.A. 42, 2849a) or with a
conformational effect (Harris and Weale, C.A. 50, 9838h); but it is consistent with a bimol. or a trimol. slow step.
The pressure coeffs. of rate consts. may be very useful in detg. the molecularity of some reactions.
Bibliographic Information
Flavor and odor components in the tomato. Spencer, Mary S.; Stanley, Wm. L. Univ. of California,
Berkeley, Journal of Agricultural and Food Chemistry (1954), 2 1113-18. CODEN: JAFCAU ISSN:
0021-8561. Journal language unavailable. CAN 49:17426 AN 1955:17426 CAPLUS (Copyright
2003 ACS)
Abstract
Unsatd. compds. were present in the fractions with typical tomato odor and with raw and green tomato odor. Also,
by their odors, spectra, and in some instances the formation of derivs., unsatd. compds. of a terpene nature, such as
citral, were present in other fractions, modifying the fractions with tomato odor. The oxidation and polymerization
of these unsatd. compds. may offer at least a partial explanation for the flavor deterioration of stored tomato
products when this occurs.
Bibliographic Information
The synthesis and polymerization of some allyl esters of carbamic acid. Gleim, C. E. Goodyear Research
Labs., Akron, O. Journal of the American Chemical Society (1954), 76 107-11. CODEN: JACSAT
ISSN: 0002-7863. Journal language unavailable. CAN 49:11789 AN 1955:11789 CAPLUS
(Copyright 2003 ACS)
Abstract
[Throughout this abstr., R = allyl.] A no. of allyl esters (I) of carbamic acids have been synthesized from ClCO2R
(II) with amino compds., generally at -10 to 10 in the presence of pyridine as an acid acceptor. NH3 passed into 368
g. II in 1000 cc. C6H6 at 25-35, the NH4Cl filtered off, washed with small amts. of C6H6, and the combined
filtrates distd. gave 255 g. (85%) H2NCO2R (III), b2 73-5, nD28 1.4520, d28 1.080. Similarly were prepd. the
following I: RNHCO2R (IV), 70%, b3 84.5-85, nD28 1.4566, d28 0.997, from II and RNH2; (NHCO2R)2, 93%,
m. 62-3, from II and N2H4.H2O; RO2CCOCH2NHCO2R, 50%, decompd. on heating, from II and
HOCH2NHCO2R (V); (RO2CCOCH2CH2)2NCO2R, 60%, decompd. on heating, nD20 1.4667, d30 1.159, from II
and (HOCH2CH2)2NH; RO2COCHMeNHCO2R, 68%, b3 165-70 (decompn.), nD25 1.5600, from II and
MeCH(OH)NH2; p-RO2COC6H4NHCO2R (VI), 77%, m. 89-90.5, from II and p-H2NC6H4OH;
RO2CNHCH2CO2R, 39%, b1 126-8, nD24 1.4653, d26 1.114, from ROH and RO2CNHCH2CO2Me, prepd. in
23% yield from II and H2NCH2CO2Me; H2NCONHCO2R, (VIa), 59%, m. 161-2, from II and urea or
RO2CNHCOCl (VII) and NH3 in Et2O. II and RO2CNHNa (VIII) gave 18% RO2CNHCO2R (IX), b3 145-7,
nD23 1.4728, d25 1.159, also obtained from VII and ROH (IX). (RO2CNHCO2 CH2)2, 55%, decompd. on
heating, was obtained from VII and (CH2OH)2 or (ClCO2)2CH2 and VIII. II and HONHCO2R (X), prepd. from
NH2OH and II in aq. Na2CO3, gave 70% RNHCO2R, b3 143-5, nD28 1.4558, d26 1.163. RONHCO2R (XI),
31%, b2 90-2, nD30 1.4569, d30 1.066, was obtained from RCl and the Na deriv. of X. RO2CONHCONHCO2R,
45%, m. 62-3, was prepd. from II and HONHCONH2. (RO)2CO and (CH2NH2)2 gave 19%
H2N(CH2)2NHCO2R (XII), b2 160, nD26 1.4775, d26 1.674, and 74% (CH2NHCO2R)2 m. 89-90. III and
CH2O in aq. K2CO3 yielded 80% HOCH2NHCO2R (V) decompd. on heating, nD28 1.4818, d28 1.120.
(RO2CNH)2CH2, 80%, m. 108-9, was prepd. from III, CH2O, and a trace HCl. III, AcH, and a trace HCl gave
similarly 80% (RO2CNH)2CHMe, m. 105-6.
III and furfural in glacial AcOH yielded 90% N,N'-dicarballyloxy-2-furylmethylenediamine. MeCH:NCO2R, 90%
m. 140.5, was prepd. from III, AcH, and concd. HCl. Allyl anhydrocitralcarbamate (XIII), 65%, b2 163-73
(decompn.), nD25 1.5170, d25 1.018, was obtained from III, citral, and glacial AcOH. III, (CHO)2, and concd. HCl
gave 50% (RO2CN:CH)2, decompd. on heating. CH2:CMeCONH2, IX, and KOBr soln. gave 82%
RO2CNHCMe:CH2, b2 60, nD28 1.5398, d30 2.017. VIII and CH2:CHCOCl in C6H6 yielded 23% (CH2:
CHCO)2NCO2R, b2 150-60 (decompn.), nD24 1.4653, d30 1.120. NCNHCO2R (XIV), m. 162-3, was prepd. in
30% yield from II and NH2CN. Concd. HCl (d. 1.10)(1200 g.) added rapidly with stirring to 3712 g. III and 3420 g.
36% CH2O, and the oil layer washed with cold H2O, cold dil. aq. NaHCO3, and H2O, and dried over anhyd.
Na2SO4 gave 3578 g. (88%) (CH2:NCO2R)x (XV), b2 185 (decompn.), nD30 1.4870, d30 1.174. II (964 g.)
added at a rate of 2 g./min. to 245 g. H2NCH2CH2OH in 712 g. pyridine at -15 to -10, the mixt. poured into cold
dil. HCl, and the oil sepd., washed with aq. NaHCO3, dried, and distd. gave 600 g. (65%) RO2CO(CH2)2NHCO2R,
b3 151-2, nD28 1.4630, d28 1.142. COCl2 passed into 202 g. III at 50-75 during 4 hrs., and the solid product
filtered off, dissolved in hot EtOH, and cooled gave 125 g. (55%) CO(NHCO2R)2, m. 70. XV gave a colorless,
transparent, insol., and infusible polymer having a Rockwell M hardness of 98, which was obtained by heating the
monomer (which may exist as a dimer or trimer) in an oven 20 hrs. at 55 in the presence of 2.5% Bz2O2. A
slightly modified A.S.T.M. test method showed the polymer to be insol. in Me2CO, 95% EtOH, gasoline, CCl4,
PhMe, and EtOAc; it was also insol. in 30% H2SO4 and 10% aq. NaOH, HCl, and HNO3; it was attacked, however,
strongly by concd. HNO3 and H2SO4. Polymeric XV showed the following phys. properties: sp. gr. of monomer
1.175, sp. gr. of the polymer 1.31, sp. gr. change during cure 15.20%, Bz2O2 concn. 2.5%, Rockwell M hardness 95,
tensile, 5000 lb./sq.
in., modulus of elasticity 240,000 lb./sq. in., modulus of rupture 10,000, abrasion resistance 6.5, dielec. const. 2.317;
sp. resistivity 2.25 1015 ohm cm., dissipation factor 2.229%. A polymeric XV having a Rockwell M hardness of
90 showed the following elec. properties: dielec. const. 2.663; sp. resistivity 2.61 1015 ohm cm., dissipation factor
1.410%. The other monoallyl esters formed thermoplastic polymers, whereas the diallyl esters formed transparent
polymers of the insol. and infusible type with Rockwell M hardness varying from 80 to 105. The monomers were
polymerized at or above their m. ps. The transparent resins having Rockwell hardness values of 75 or more were
glasslike in nature. The polymer hardness was found to increase until a max. degree of polymerization was
reached. Too high a temp. or too high a catalyst concn. (Bz2O2 or Me3COOH) tended to cause polymer
discoloration and cracking. The conversions to polymers were practically quantitative since the monomer volatility
decreased rapidly as the polymerization progressed. The monomers IV, XI, XII, VI, VIa, XII, and XIV failed to
polymerize when heated for several hrs. with peroxide catalysts. Most of the I will undergo copolymerization with
other monomers to give a modification of polymer properties. Some I have been particularly useful as cross-
linking agents and a no. of copolymers have been prepd.
Bibliographic Information
Concentration of acrolein and methacrolein. Howlett, John; Lombard, Cecil A. (The Distillers Co. Ltd.).
(1953), GB 687852 19530225 Patent language unavailable. CAN 48:49526 AN 1954:49526
CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
GB 687852 19530225 GB
Abstract
Acrolein and methacrolein produced by catalytic oxidation of propene and isobutene, resp., are recovered by distn.
at 200-400 mm. and a pH of 5-8. Use of reduced pressure minimizes the formation of undesired polymers during
the distn. By introducing a small amt. (5% of the amt. equiv. to the theoretical O requirements) of hydroquinone to
the still-head, polymerization can be practically eliminated.
Bibliographic Information
Note about the constitution of the essential oil of Homalomena rubescens. Pallaud, R. Bulletin de la
Societe Chimique de France (1953), 841-2. CODEN: BSCFAS ISSN: 0037-8968. Journal language
unavailable. CAN 47:75209 AN 1953:75209 CAPLUS (Copyright 2003 ACS)
Abstract
cf. Sadgopal and Kuldip Bhatia, C.A. 47, 6095a. The essential oil distd. from the rootstocks was a slightly
yellowish, slightly viscous liquid with a pleasant odor reminiscent of that of the essence of coriander. Its analytical
consts. were d15 0.8935, []D -68', nD 1.4719, acid no 0.4, ester no. 1.4, carbonyl no. 11.1 (in the cold), 22.4
(warm), ester no. after formylation in the cold 241.3, free alc. content expressed as linalo.ovrddot.ol 75.3%. Its
soly. was, in 65% alc.: 4 vol. with pptn. of paraffins, in 80% alc.: in all proportions before pptn. of paraffins, in 90%
alc.: in all proportions without cloudiness. The oil (100 g.) was fractionated in a Widmer column under a 10-mm.
vacuum. The following fractions were obtained: I 21, 1.5 g.; II 84-86, 48.5 g., d10 0.868, nD 1.4669, []D -
1430'; III 86-89, 13.6g.,d100.869, nD 1.4702, []D -1312'; IV 101-6, 6 g., d10 0.907, nD 1.4791, []D -019'; V
106-109, 4 g., d10 0.910, nD 1.4782, []D -015'; VI 120-150, 13.5 g., d10 0.904, nD 1.502, []D -015'; dry
residue 9.5 g. Fractions II and III were linalo.ovrddot.ol, characterized as the phenylurethan, m. 65, and the
naphthylurethan, m. 53, and by the formation of citral (semicarbazone m. 71) by chromic oxidation. Fraction II
contained no esters; fraction III contained only 2.3% expressed as linalyl acetate. A small quantity of linalyl acetate
was found after several refractionations of III and IV. The alc. was characterized as above and, in solns. from the
sapon., acetic acid was identified by the formation of its p-bromophenacyl ester, m. 85. During the purification of
linalo.ovrddot.ol, -terpineol was isolated in the alcs. at the end of the fractionation. It was characterized by the
phenylurethan, m. 111, and its naphthylurethan, m. 149. All m.ps. were by mixed m.-p. detns. with a Maquenne
block. Linalo.ovrddot.ol content was detd. by formylation (in the presence of pyridine). The essence contained
about 60% l-linalo.ovrddot.ol and traces of linalyl acetate and -terpineol.
In the work referred to above, only 40% of linalo.ovrddot.ol was found; this is explained as the result of distn. of
the oil at normal atm. pressure, which caused polymerization, and by the use of an analytical method not considered
suitable for the detn. of tertiary alcs.
Bibliographic Information
Aromatics and acetylene. Okazaki, Monji. Koryo (1953), No. 23 10-13,50. CODEN: KORYAR
ISSN: 0368-6558. Journal language unavailable. CAN 47:72390 AN 1953:72390 CAPLUS
(Copyright 2003 ACS)
Abstract
The advantages of using C2H2 are illustrated for the synthesis of Me heptenecarbonate, linalo.ovrddot.ol, citral,
indole, and PhCH:CHCHO; and detailed reactions are shown for vinylation, ring formation by polymerization,
ethenylation, and carbonylation made possible by Reppe's discovery.
Bibliographic Information
Shortstopping vinyl chloride polymerizations. Seymour, Dexter C. (United States Rubber Co.). (1952),
US 2616887 19521104 Patent language unavailable. CAN 47:33855 AN 1953:33855 CAPLUS
(Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
US 2616887 19521104 US
Abstract
Unsatd. aldehydes, e.g., cinnamaldehyde, crotonaldehyde, acrolein, methacrolein, tiglic aldehyde, citral, citronellal.
Bibliographic Information
Organic sulfur compounds. III. Thiosemicarbazones, hydrazothiazolinones, and alkyl-1-imino-2,3-diaza-6-
thiacyclohexan-4-ones. Chabrier, Pierre; Cattelain, Eugene. Faculte pharm., Paris, Bulletin de la
Societe Chimique de France (1950), 48-61. CODEN: BSCFAS ISSN: 0037-8968. Journal language
unavailable. CAN 45:3566 AN 1951:3566 CAPLUS (Copyright 2003 ACS)
Abstract
cf. C.A. 44, 1452g, 5347g. Thiosemicarbazones of many aldehydes and ketones have been prepd. and converted to
heterocyclic derivs., hydrazothiazolinones (I), by the action of -halo acids (ClCH2CO2H was used for the present
work). To 5.7 g. (0.05 mole) C6H13CHO in 75 cc. alc. at 95 was added 4.55 g. (0.05 mole) H2NCSNHNH2 and
then 0.5 cc. AcOH, the mixt. boiled 1 hr., filtered, the filtrate evapd., the residue crystd. by stirring, taken up in
C6H6, and C6H6 contg. a little petr. ether added, giving heptanal semicarbazone (II), m. 78-9. To 2 g. II in 50 cc.
alc. at 95 was added 2 g. NaOAc and 2 g. ClCH2CO2H, the mixt. boiled 1 hr., cooled, and the ppt. filtered, washed
with alc. at 95 and H2O, and recrystd. from alc. (C6H6 was a common solvent for many others), giving colorless
crystals of 2-(heptylidenehydrazino)-4(5H)-thiazolone, m. 135-7 (I; R = Me(CH2)5CH). The reaction is very
general and the yields are high. HCH:NNHCSNH2, m. 155-6, failed to give a I, probably because of
polymerization. The reaction was applied to the following addnl. compds. (m.p. of thiosemicarbazone and
hydrazinothiazolone, resp., given): PhCH2CHO, 147-8, 158-60; PhCH:CHCHO, 95, about 240; citral, 107-8,
182; p-O2NC6H4CHO, 230-1, 265; p-AcNHC6H4CHO, 207, 294; vanillin, 193-4, 253-4; piperonal, 182-3,
257; -HOC6H4CHO, about 230, about 255; 5,2-Br(HO)C6H3CHO, about 230, 300; 3,5,2-I2(HO)C6H2CHO,
225, 245-7; furfural, 148-9, 223-4; Me2CO, 179, 181; MeCOAm, 73, 110; diiso-Bu ketone, 103-4, 118;
PhAc, 108, 215; p-MeC6H4Ac, 158-9, 215-20; Me naphthyl ketone, 175, 203-5; p-MeOC6H4Ac, 174-5,
192-5; PhCOEt, 113-14, 145-6; PhCOCHMe2, 160-5, 240 (decompn.); PhCOPr, 92 (from the table), 122;
Ph2CO, 160-1, 170; cyclopentanone, 155-7, 215-18; cyclohexanone, 148, 289-90; 2-methylcyclohexanone,
150-1, 293; 2-acetylthiophene, 134-5, 175-6; 2-acetyl-5-nitrothiophene, 152, 242. In addn., a compd. called
isobutyrophenone gave a semicarbazone, m.
121-2, and thus is distinct from the above isopropyl phenyl ketone. The thiazolonylhydrazone of p-iso-
PrC6H4CHO m. 199. If the ring N in I bore a substituent, both double bonds would have to be exocyclic; in order
to test this point and the correctness of formula I, 4-substituted thiosemicarbazides were used. To 2 g.
NH2NHCSNHMe and 3.5 g. NaOAc in 40 cc. alc. at 95 was added 2.5 g. ClCH2CO2H, the soln. boiled 40 min.,
and the ppt. filtered, washed with alc. at 95 and cold H2O, giving 1-methylimino-2,3-diaza-6-thiacyclohexan-4-
one, m. 284 (III; R = Me). Similarly NH2NHCSNHEt gave the 2-ethylimino analog (III; R = Et), m. about 230.
Thus when the double bond can not be in the ring the reaction takes a new course and yields a new heterocyclic ring
system. Tests given for distinguishing between thiosemicarbazones and I include Fe(ClO4)3 (I gives a color).
Iodine in alc. gives a blood-red color with I, and Pb acetate desulfurizes some semicarbazones. Solubilities for the
new compds. are given.
Bibliographic Information
Essential oil from the leaves of Blumea lacera. Baslas, K. K.; Deshapande, S. S. Agra Coll., Agra, J.
Indian Chem. Soc. (1950), 27 25-8. Journal language unavailable. CAN 44:36772 AN 1950:36772
CAPLUS (Copyright 2003 ACS)
Abstract
cf. C.A. 3, 1908. The oil consisted of 66% cineol (I), 10% d-fenchone (II), and about 6% citral (III). The oil was
obtained by steam-distn. of the leaves in 0.5% yield, with d39 = 0.982, nD = 1.490, and []D39 = 31.6. The
steam distillate was extd. with CCl4, dried, solvent removed, and fractionated into 3 portions. Fraction 1 was very
ordorous, b. 178, absorbed Br, and gave no reaction with NOCl, Fehling soln., ammoniacal AgNO3, or
NH2NHCONH2. This fraction was I, as shown by formation of a solid addn. compd. with sirupy H3PO4, and a
cryst. deriv. with resorcinol, m. 87-90 after two crystns., which again liberated I on warming with aq. NaOH.
Fraction 2 was redistd., b30 91 and 192 at atm. pressure. Analysis indicated the formula C10H16O. This
fraction did not reduce Fehling soln. or ammoniacal AgNO3 and had no characteristic OH groups. It formed an
oxime, m. 163; the semicarbazone m. 186-7 on crystn. Comparison with a known sample indicated II. Fraction
3, b30 120-35, was unstable when distd. at atm. pressure where it b. 230, and tended to polymerize. This fraction
reduced Fehling soln., formed an addn. product with NaHSO3, and gave a semicarbazone, m. 163, indicating III.
Bibliographic Information
Essential oil from the leaves of the bael fruit (Aegle marmelos). Baslas, K. K.; Deshapande, S. S. Agra
Coll., Agra, India. J. Indian Chem. Soc. (1949), 26 231-4. Journal language unavailable. CAN
44:16241 AN 1950:16241 CAPLUS (Copyright 2003 ACS)
Abstract
Steam distn. of the leaves of the tree Aegle marmelos (family, Rutaceae) gave an essential oil in 0.6% yield, d26
0.8476, nD31 1.4750, []D 52.1, acid value 2.9, sapon. value 16.1, citral content 3.76% (cf. Radcliffe and Swann,
C.A. 22, 1747). Fractional distn. of the oil (80 ml.) gave 3 fractions: (I) 45 ml. (56%), b130 80-104, b. 173-4; (II)
17 ml. (21%), b130 104-30, b. 205-8; and (III) 7 ml. (9%), b130 130-60, b. above 210 (polymerization).
Fraction I, extd. with 50% aq. resorcinol, left -d-phellandrene, b. 173-4, nD31 1.477, []D 49.1; nitrosite m.
105, and on repptn. from CHCl3 with MeOH, m., 114, []D -47 (in CHCl3) which, in 3 days, changed to +42.6.
The aq. resorcinol soln. with alkali gave cineole, b. 176, which formed a semisolid mass with H3PO4, and yielded
a characteristic yellowish green cryst. addn. compd. with iodol (tetraiodopyrrole) (cf. Bertram and Walbaumm, Arch.
Pharm. 235, 178(1897)). Fraction II, treated with a cold satd. Na2SO3 soln. and then an equiv. amt. of HOAc, gave
the bisulfite addn. compd. of citronellal; semicarbazone, crystd. from alc., m. 84 (citronellal semicarbazone, m.
86). Fraction III also gave a bisulfite addn. compd. and a semicarbazone, m. 163; it consisted of citral (citral
semicarbazone, m. 164). Fractions II and III both gave usual aldehyde reactions.
Bibliographic Information
Vitamin E. XLI. Synthesis of 1-chloro-3,7,11,15-tetramethylhexadecan-3-ol and its condensation with
trimethylhydroquinone to form -tocopherol. Smith, L. I.; Sprung, J. A. J. Am. Chem. Soc. (1943), 65
1276-83. CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN 37:33669 AN
1943:33669 CAPLUS (Copyright 2003 ACS)
Abstract
cf. C. A. 37, 2372.4. In the following synthesis citral (I) was chosen as the most promising starting material for the
synthesis of any substance contg. 20 C atoms with a regular sequence of "isoprene" units. An ether of
(CH2)3(OH)2 was required which could be produced in good yield, would not be readily cleaved by PBr3 or PCl3
or when the Grignard reagent is formed and yet could be cleaved fairly readily later in the synthesis. The Me, Et
and PhCH2 monoethers result in 38, 64 and 73% yields; the Et ether was chosen because the yield of the 3 bromides
were 27, 70 and 34% (3-benzyloxypropyl bromide, b8 130-2) and of EtO(CH2)3Cl was 67%. CH2:CHAc did not
react well with laurylmagnesium bromide (II) because of polymerization but the reaction product with HCl
(ClCH2CH2Ac (III)), prepd. in 67% yield at 0, was satisfactory. It was necessary to use carefully purified I and to
purify the pseudoionone (IV) through the NaHSO3 compd., the yield of IV being about 45% (based upon I).
Reaction of 96 g. IV and 100 g. EtO(CH2)3Br in 375 cc. ether with 15.2 g. Mg, with final heating of the product at
90-5 for 30 min., gives 52% of the 4,8,12-trimethyl-3,5,7,11-tridecatetraen-1-ol Et ether, Me2C:CHCH2CH2CMe:
CHCH:CHCMe:CHCH2CH2OEt (V), lemon-yellow, b3 163-5, n25D 1.5242; it forms a sticky, glassy solid on
exposure to air. The Me ether (53.5%) b3 150-60 and the benzyl ether (49%) b3 210-20. Br(CH2)3OAc could
not replace Br(CH2)3OEt in the above reaction. Catalytic reduction of V with Raney Ni at 125 and 2000 lb. H
pressure (3 mols. of H are rapidly adsorbed (1 hr.) and the reduction is completed by heating at 125 for 1 hr. after
apparent absorption of H has ceased) gives 82% of 4,8,12-trimethyl-1-tridecanol Et ether (VI), b3 138-40, n25D
1.4370. Cleavage of VI to 1-bromo-4,8,12-trimethyltridecane (VII), b3 138-40, n25D 1.4598, was very slow and
incomplete when carried out in open vessels; when dry HBr was passed through VI at 135 for 6 hrs. 27% cleavage
occurred; action of 48% HBr was much slower; addn.
of a great excess of AcOH accelerated the reaction but 12 hrs. at 115 were required for 85% cleavage; when the
cleavage was carried out under pressure, in AcOH contg. 3 mol. of dry HBr per mol. VI, the reaction was complete
(96%) in 6 hrs. at 150. The Me ether could be cleaved (95%) in 4 hrs. at 180 and the benzyl ether in 5 hrs. in
refluxing AcOH-HBr (these ethers were not characterized). The Grignard reagent from 41 g. VII and 20 cc. AcH in
ether give 70% of 6,10,14-trimethyl-2-pentadecanol (VII), b3 150-5, n25D 1.4448. Oxidation of VII with
Na2Cr2O7 in dil. AcOH-H2SO4 at 40 gives 75% of 6,10,14-trimethyl-2-pentadecanone (phytol ketone), b3 150-2,
n25D 1.4433. EtMgBr and III give 51% of 1-chloro-3-methyl-3-pentanol (VIII), b50 104-5, camphor-like odor.
VIII (3.7 g.), 4 g. trimethylhydroquinone (IX) and 4 g. ZnCl2 in 15 cc. AcOH, refluxed 1 hr., the product decompd.
with H2O, extd. with petr. ether and the oil refluxed in MeOH-KOH for 30 min., give 2-ethyl-2,5,7,8-tetramethyl-6-
hydroxychroman, m. 60-1. III and II give 34.5% of 1-chloro-3-methyl-3-pentadecanol, b3 165-70. The
Grignard reagent from crude VII (75% VII and 25% VI) and III give 38% of 1-chloro-3,7,11,15-tetramethyl-3-
hexadecanol(isophytol hydrochloride) (X), b2 173-5, n25D 1.4620. Reaction of 12 g. X, 5 g. IX and 2.5 g. ZnCl2
in 20 cc. AcOH (refluxing 1.5 hrs.), followed by hydrolysis with MeOH-KOH, gives 70% of -tocopherol. The
above reactions may constitute a new synthesis of phytol. They also make practicable the tocopherol synthesis of
Smith and Miller (C. A. 36, 1933.2).
Bibliographic Information
Investigation of the chemical constituents of distilled lime oil (Citrus medica, L., var. Acida, Brandis) (Citrus
aurantifolia, Swingle). Guenther, Ernest S.; Langenau, Edward E. J. Am. Chem. Soc. (1943), 65 959-
63. CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN 37:23955 AN
1943:23955 CAPLUS (Copyright 2003 ACS)
Abstract
The oil studied was distd. in Mexico from the juice of the green crushed fruit of Citrus medica, L., var. Acida,
Brandis; d15 0.866, nD20 1.4761, D20 41.6, soly. at 20 4.5-5 vols. of 90% EtOH, aldehyde (as citral) 1.15%;
this was sepd. into 4 fractions and a residue with a com. still with a 6-ft. column: I, 75%, up to 68 at 14 mm.; II
2.4%, 68/14 mm. to 76/12 mm.; III 14.9%, 76-105/12 mm., IV 3.8%, 105-29/12 mm.; residue (V) 3.4%, above
129/12 mm. Phys. properties of these fractions are given. The following products were identified by their phys.
consts. and the prepn. of derivs.; the details are not abstracted. I: - and -pinene, furfural, octyl aldehyde, d-
limonene and dipentene; II: nonylaldehyde and borneol; III: decylaldehyde, geraniol, citral, linalo.ovrddot.ol and -
terpineol; an unidentified aldehyde with an odor suggestive of cumaldehyde was not obtained in a pure state; it is
very susceptible to polymerization on exposure to air; the NaHSO3 compd. is very sol. IV: lauric aldehyde and
bisabolene; V: lauryl alc., bisabolene and an azulenic compd. The acidic fractions contained acetic, octylic and
decylic acids and a trace of a phenol. Borneol, geraniol and -terpineol occur as free alcs. and possibly also as
esters; lauryl alc. probably occurs as an ester. Phellandrene, p-cymene, terpinene, cadinene or high-boiling
paraffinic hydrocarbons could not be detected.
Bibliographic Information
Isocitral from enolic citral acetate. Schmidt, Harry. Ber. Schimmel & Co. Akt.-Ges. (1939), 114-16.
From: Chem. Zentr. 1940, I, 196. Journal language unavailable. CAN 36:10073 AN 1942:10073
CAPLUS (Copyright 2003 ACS)
Abstract
cf. C. A. 33, 3331.7. When citral, RCH2CMe:CHCHO (R = Me2C:CHCH2) (I), is enolized and the enolic citral
acetate (II), RCH:CMeCH:CHOAc or RCH2C(:CH2)CH:CHOAc, sapond., the reformation of I is not to be
expected. The double bond can be shifted in 2 directions with the formation of RCH:CMeCH2CHO (III) or
RCH2C(:CH2)CH2CHO (IV). An unsuccessful attempt to carry out this sapon. was made by Semmler and
Schossberger (cf. C. A. 5, 2825-6). By heating II with abs. alc., or, better, with MeOH and Al alcoholate, exchange
of the ester radicals was effected with the formation of the alkyl acetate and isocitral. With the use of MeOH
practically no reduction by the Meerwein-Ponndorf reaction occurred. Under the long-continued action of (iso-
PrO)3Al the isocitral polymerized. When oxidized with KMnO4 and CrO3, isocitral yielded no ketoadipic acid but
rather gave acetone and HOAc. It is therefore to be represented by III and not by IV. The crystal form of the
semicarbazone indicated a homogeneous compd. Nothing can be said regarding the relation between isocitral and
the isogeraniol of Semmler and Schossberger. Isocitral (III) was prepd. by boiling II with (iso-PrO)3Al and abs.
MeOH together with AcOMe for 14 hrs. It is a faint yellow, mobile oil having a fresh, lemon odor, b12 95-7, d.15
0.890, n.D20 1.4838. It did not react with Na2SO3 + NaHCO3 and gave no cryst. condensation product with
CNCH2CO2H. The semicarbazone forms platelets m. 140 and is decompd. even by oxalic or phthalic acids with
the formation of terpenes and products of resinification. -Isocitryl--naphthocinchoninic acid, obtained from III,
pyroracemic acid, and 2-naphthylamine, m. 195-6. -Citryl--naphthocinchoninic acid, prepd. from citral or
neral, m. 202.
Bibliographic Information
Ocimum canum oil of north India. Rakshit, Jitendra N. Perfumery Essent. Oil Record (1938), 29 402.
Journal language unavailable. CAN 33:18057 AN 1939:18057 CAPLUS (Copyright 2003 ACS)
Abstract
The constituents of the essential oils obtained from this shrub grown in various parts of the world have been detd.
(cf. Gildemeister and Hoffmann, Die Atherischen .ovrddot.Ole, C. A. 25, 3775). They vary considerably and those
for a north Indian oil are now recorded. The shrub grows both wild and cultivated. Its seeds are used for the
prepn. of cooling drinks and also as a diuretic. The oil has so far not been utilized. That used in these expts. was
distd. in steam from mature plants (leaves, soft twigs and flowering tops, all green) in a yield of 0.38%. It was very
pale yellow, with a strong but not unpleasant odor, differing considerably from that of Ocimum basilicum. The
following consts. were observed: d2020 0.89142, nD20 1.4842, D20 -2.66, acid no. 3.4, aldehyde 60%, phenol
1.2%, ester no. 9.4, methyl no. 2.0. After removal of the free acids by washing the oil with aq. Na2CO3 and the
phenols by aq. NaOH, the oil was shaken with freshly prepd. aq. Na2SO3 to sep. the citral. After removal of the
undissolved oil, the aq. soln. was shaken with C6H6, then made alk. with aq. NaOH. In this manner citral was
isolated (129 cc. from 275 cc. of the original oil). The oil, which did not react with Na2SO3, was distd. in steam to
remove a nonvolatile portion (15 cc.), then shaken at 0 with aq. NaHSO3. The cryst. NaHSO3 compd. which seps.
was collected, washed with H2O, alc., and Et2O, and the citronellal regenerated by alkali. It b. 197 (yield 15.7%).
The oil remaining after treatment with NaHSO3 was distd. under reduced pressure yielding l-linalo.ovrddot.ol
(10.2%), together with a high-boiling residue consisting of Me cinnamate and an unsaponifiable oil probably a
polymerized terpene. The Na2CO3 washings (see above) were acidified and distd. in steam yielding a mixt. of
acids. The fraction sol. in H2O was identified as AcOH, while analysis of the Ag salt of the insol. acid suggested
that it was citronellic acid. The aq. NaOH was concd. on the H2O-bath when an oil sepd.;
this was identified as eugenol. From the aq. soln. a further quantity of a phenol was sepd. giving with aq. FeCl3 a
bluish violet coloration. The amt. was too small to permit of its identification.
Bibliographic Information
A reagent for oxidizing substances. Pratesi, Pietro; Celeghini, Rina. Gazz. chim. ital. (1936), 66 365-
70. Journal language unavailable. CAN 31:18264 AN 1937:18264 CAPLUS (Copyright 2003 ACS)
Abstract
The oxidation of 2,5-bis[2,4-dimethyl-N-pyrryl]-3,6-dibromohydroquinone (I) to the corresponding intense blue
quinone (II) can be utilized as a characteristic and sensitive reaction of many oxidizing agents. The specific
reactions of I (0.5-1% soln. in C5H5N) with H2O2, BzO2H (III), o-HO2CC6H4CO2OH (IV), Et2O2 (V), Bz2O2
(VI), [PhCH2CH2CO2-]2 (VII), [o-HO2CC6H4CO2-]2, (VIII) and [o-EtO2CC6H4CO2-]2 (IX) were studied. In
these reactions the solvent used for the sample should be tested because in some cases exposure to air gives a pale
bluish color. The reaction is sensitive to 0.05 mg. of III, and with IV to IX the reaction is also sensitive, so that it is
of more general application than KI. The general nature and sensitivity offers a convenient means of detecting the
intermediate formation of peroxides or the activation of mol. O in autoxidation and polymerization reactions, e. g.,
III in the autoxidation of BzH by atm. O, and peroxides in the autoxidation of turpentine or pinene, and in the
polymerization of styrene in air. Previously unknown cases include the activation of mol. O in the autoxidation of
citral, linalool and pulegone in air. The color reaction of I is particularly adapted to reactions in nonaq. media.
Various quinones, e. g., benzo-tolu-, thymo- and 2,5-dibromoquinone (X), also give a pos. reaction in C5H5N,
AcOEt, dioxane and EtOH, as also do certain ions and oxidizing elements, e. g., I in EtOH or dioxane detects 0.002
mg. of ferric, ferricyanide, Cl or Br ions in water. The reaction is especially useful for detecting ferric Fe in the
presence of large quantities of other nonoxidizing ions (alkali, alk. earth, ferrous, manganous, Mg, Zn, Cd, Al and
chromic). The oxidation of I to II by H2O2 and III-IX depends on the solvent, e. g., in C5H5N oxidation is
complete, whereas in EtOH, dioxane and AcOEt only VI, VII and IX react. No relation between this different
behavior and general structure was evident. In the prepn. of I (cf. C. A.
31, 1024.7), it is better to use an excess of 2,4-dimethylpyrrole (XI) (2 mols.), for then 12 g. of X in Me2CO and 8.6
g. of XI yield, on standing 1 day, 8 g. of I. On exposure to air, solns. of I oxidize and become distinctly blue,
especially with C5H5N, and alk. hydroxides and NH4OH accelerate greatly this oxidation, in accord with the
general behavior of hydroquinones. Both I and II are stable to HCl and H2SO4, so that the color reaction may be
carried out in their presence. HNO3, however, has a profound effect on the reaction.
Bibliographic Information
The formation of enamines and allene amines from ,-unsaturated aldehydes and secondary bases.
Mannich, C.; Handke, K.; Roth, K. Ber. (1936), 69B 2112-23. Journal language unavailable. CAN
30:61872 AN 1936:61872 CAPLUS (Copyright 2003 ACS)
Abstract
Well-defined substances can be obtained in good yields from ,-unsatd. aldehydes and secondary aliphatic amines.
In their prepn. (CH2:CHCHO, MeCH:CHCHO, PhCH:CHCHO, citral, were used as the aldehyde, NHMe2 and
piperidine as the base) 2 points must be kept in mind: all the water must be removed by the addn. of much K2CO3,
and the temp. must be kept within definite limits. Below -10 the reaction does not take place, and above 20 the
yields are decreased by the formation of resinous products. One mol. aldehyde, RCH:CHCHO, reacts with 2 mols.
amine, NHR2, to form an unsatd. 1,3-diamine, RCH(NR2)CH:CHNR2. The new, almost always oily compds. are
quite sensitive. They darken quickly in the air and decompose on heating, so that many cannot be distd. even in
vacuo. They are readily hydrolyzed; when they are shaken with water, the odor of the aldehyde component is
evolved, as also when they are dissolved in acids. The amine can be recovered quantitatively from the acid soln.,
and when the hydrolysis is effected in the presence of dimethone, the aldehyde can also be isolated as the dimethone
compd. The 2 basic groups are apparently split off not simultaneously but progressively, the one next to the double
bond first. Cautious reduction of C5H10NCH2CH: CHNC5H10 (I) and MeCH(NC5H10)CH:CHNC5H10 (II) with
Na-Hg in acid soln. gives considerable 3-piperidinopropanol (III) and 3-piperidino-1-butanol (IV), resp. On
catalytic hydrogenation in cyclohexane, I and II and the corresponding NMe2 compds. yield 70-93% of the satd.
1,3-diamines, but there is also some cleavage of the N on C atom 3: RCH(NR2)CH:CHNR2 RCH2CH2CH2NR2
+ NHR2; in abs. alc. far more monoamine is obtained than in cyclohexane. The compd.
PhCH(NC5H10)CH:CHNC5H10 (V) obtained from PhCH:CHCHO and piperidine gives only the monoamine
PhCH2CH2CH2NC5H10 (VI) on hydrogenation because V is a PhCH2NH2 deriv. in which the basic group is
readily replaced by H. Me2NCH2CH:CHNMe2 (VII) and MeCH(NMe2)CH:CHNMe2 (VIII), because of their
low m. ps., can be distd.
in vacuo. At higher temps., these compds. decompose into a mol. of NHMe2 or piperidine and a doubly unsatd.
monoamine. I should yield piperidinoallene (IX) but the IX was obtained only in polymerized, nondistillable form.
II, on the other hand, gave in satisfactory yield 1-piperidino-8-methylallene (X), sensitive to air and distillable in
vacuo; on cautious acid hydrolysis (in the presence of methone) X yielded MeCH: CHCHO and on hydrogenation
gave 1-piperidinobutane. V decomposes into an allene base with special ease; with picric acid it gives piperidine
picrate and the picrate of the base PhCH:C:CHNC5H10 (XI), whose HI salt is also obtained, along with
dimethylpiperidinium iodide, from V with MeI. These reactions must be carried out in the absence of water, as the
salts of XI are easily hydrolyzed to PhCH:CHCHO. The HI salt is hydrogenated in abs. alc. to 1-phenyl-3-
piperidinopropane (XII). Citral with NHMe2 gives no diamine, which is probably too unstable, and there is
obtained directly the triply unsatd. monoamine Me2C:CHCH2CH2CMe:C:CHNMe2 (XIII). The NMe2 is very
easily hydrolyzed off with formation of a mixt. of much citral a and a little citral b. XIII can be hydrogenated in 3
stages to a hexahydro deriv.; the 1st 1.25 mols. are absorbed rapidly, when the hydrogenation is so slowed up by the
deposition of resinous products on the catalyst that it is well to stop the reaction. The double bond on C atom 1 is
apparently satd. during this stage, for the dihydro base (XIV) is not hydrolyzed by acids. On further hydrogenation
the 2,3-double bond is satd. The tetrahydro base (XV) takes up the last mol. of H very slowly to give the known
Me2CH(CH2)3CHMe(CH2)2NMe2 (XVI). XIV on Hofmann degradation should give a terpene
Me2C:CHCH2CH2CMe:C:CH2 but the product (XVII) gave, among other products, malonic acid on oxidation and
reacted in benzene with maleic anhydride. Apparently a shifting of a double bond takes place and XVII is probably
ocimene or myrcene.
XIV and XV readily add water in the presence of acids to form the alc. bases
Me2C(OH)CH2CH2CH2CMe:CHCH2NMe2 (XVIII) and Me2C(OH)CH2CH2CH2CHMeCH2CH2NMe2 (XIX).
1,3-Bis(dimethylamino)-1-propene VII (19 g. from 14 g. CH2:CHCHO in 30 cc. ether dropped, along with 60 g.
K2CO3 in small portions, with vigorous stirring in the course of 1.5 hrs. into 60 g. 45% aq. NHMe2 at -5 to 0),
b13 52-4. 1,3-Dipiperidino-1-propene (I) (75% yield), b12 150-2 when distd. rapidly. III, b12 102-4; benzoate-
HCl, m. 186. 1,3-Bis(dimethylamino)-1-butene VIII, b17 64 (65% yield). 1,3-Dipiperidino-1-butene II, begins
to decompose 130 and could not be distd. IV, bvac 100-30; nitrobenzoate-HCl, m. 176, X (8.3 g. from 22.5 g. II),
b15 98; chloroaurate, yellow, m. 91. 1,3-Dipiperidino-1-phenyl-2-propene (V) (80% yield), sinters 55-6, m.
clear 58. 1-Phenyl-3-piperidinopropane VI (4 g. from 20 g. V), b2.5 127-30. 1-Phenyl-3-piperidinoallene XI,
isolated as the picrate, m. 164; HI salt, golden yellow, sinters 206-7, m. 211-12 (decompn.). XII, b15 149; HCl
salt, m. 184-5; HI salt, m. 138; methiodide, m. 134-5. 1 - Dimethylamino - 3,7 - dimethyl - 1,2,6 - octatriene
XIII (50% yield), b12 123-4, decomposes above 190. The 2,6-diene XIV (36 g. from 45 g. XIII), b16 103,
characterized as the methiodide, m. 178-80, and the 2- octen-7-ol XVIII (14 g. from 18 g. XIV), b11 125 (HCl
salt, m. 110-11; methiodide, m. 111-12). XVII, b15 56-8, b. 165-8 (partial resinification), is reduced by H with
Pt oxide in alc. to 2,6-dimethyl-2-octene, b. 162-3, which forms a dibromide, b15 126-7; the octene and the
dibromide are both reduced to 2,6-dimethyloctane, b. 157. 1-Dimethylamino-3,7-dimethyl-6-octene XV, b16 99-
100; HCl salt, m. 167; methiodide, m. 220-2. Hofmann degradation of the methiodide gives 2,6-dimethyl-2,7-
octadiene, b. 160-1 d20 0.7580, nD 1.4358, identical with -linalolene. XIX, b14 128-30; HCl salt, hygroscopic,
m. 95; methiodide, m. 100-1. XVI, b15 95; HCl salt, m. 186-7; methiodide, m. 242.
Bibliographic Information
Aldehyde condensations with secondary amines (Knoevenagel reaction). Kuhn, Richard; Badstubner,
Werner; Grundmann, Christoph. Ber. (1936), 69B 98-107. Journal language unavailable. CAN
30:22310 AN 1936:22310 CAPLUS (Copyright 2003 ACS)
Abstract
The action of secondary amines (piperidine) on AcH or mixts. of AcH and MeCH:CHCHO (I) has thus far been the
most profitable method of prepg. aliphatic polyene aldehydes (C. A. 25, 5891). In an attempt to condense I with
itself in the same way to octatrienal, Me(CH:CH)3CHO (II), however, no elimination of water was observed and no
II could be detected with N2H4 or malonic acid. Bernhauer and Woldan (C. A. 26, 4581) questioned this and,
without describing their expts., reported that I can be condensed to II. These apparently contradictory observations
have now been cleared up. Pure I does not undergo condensation in the presence of piperidine, but if it is exposed
to sunlight or for a short time to the light of a quartz lamp, addn. of a drop of piperidine is quickly followed by the
appearance of a brown color and the splitting off of water. It was readily shown that the illumination does not
destroy a substance which prevents condensation, but produces a compd. which is indispensable for condensation.
This is probably MeCH:CHCO2H (III), produced by autoxidation, for the same result is obtained by treating II in
the dark with a little III. If II "activated" by illumination or addn. of III is purified by adding NaOH, extg. with
ether and redistg., it again becomes entirely "inactive." III can be replaced by AcOH, citric acid, BzOH, cholic
acid, etc., or, less satisfactorily, by phenols. In other words, it is not piperidine but piperidine salts which effect the
condensation, a fact which was not unknown, as is shown by various observations recorded in the literature. For
the prepn. of II piperidine acetate (an equimol. mixt. of piperidine and AcOH dild. with a little alc.) is recommended.
This catalyst can also be used for the condensation of BzH with I to phenylpentadienal, with yields about equal to
those obtained by the usual NaOH method, while it is much superior to NaOH for the condensation of citral with
AcH to citrylideneacetaldehyde (IV).
Among the products of the reaction of piperidine on AcH + I is a small amt. of decatetraenal, Me(CH:CH)4CHO
(V) (Reichstein and Trivelli, C. A. 27, 266), probably formed according to both of the reactions I +
Me(CH:CH)2CHO (VI) V and AcH + II V. As considerable amts. of VI and III are formed, it is advisable to
recondense the tailings of the VI fraction and the III fraction with AcH, thereby greatly increasing the yield of V.
Condensation of V with malonic acid in pyridine gives a 5-fold unsatd. dicarboxylic acid, decarboxylated (but with
great loss) by dry heating to dodecapentaenoic acid, Me(CH:CH)5CO2H (VII); much better yields are obtained by
boiling the dicarboxylic acid with AcOH-Ac2O. The IV obtained by the authors (in 30% yield) had a peculiar
persistent pear odor and a much higher b. p., a higher d. and a somewhat higher n than that obtained by v. Braun and
Rudolph (C. A. 29, 452.4) from citrylideneacetic acid by their CrCl2 method and which they describe as having a
strong lily-of-the-valley odor. They believed their product was a mixt. of cis-trans isomers and the present authors
made numerous attempts to rearrange their own IV under the purest N or in vacuo with I, sunlight, ultraviolet light,
etc., but never observed the lily-of-the-valley odor. That their product has the structure assigned to it was shown by
(1) alk. degradation to citral, AcH and methylheptenone, and (2) oxidation with Ag2O and subsequent catalytic
hydrogenation to dl-,-dimethylcapric acid (VIII). Reduction with (iso-PrO)3Al and iso-PrOH gave a
citrylidene.ovrddot.ethyl alc. (IX) having a rose-like odor more persistent than that of geraniol. V,m. 107-7.5;
hydrazone, egg-yellow, begins to sinter and turn brown about 190, is completely resinified and black at 280,
dissolves in concd. H2SO4 with dark wine-red color, forms a brownish red soln. with SbCl3 in CHCl3. VII, m.
247 (decompn.), sol. in concd. H2SO4 with brown-red color, forms with SbCl3 in CHCl3 a brown-yellow soln.
becoming light yellow after long standing and bringing to a boil; Me ester, yellow, m. 190.5, polymerizes and
autoxidizes on long standing in the air to a viscous brown mass insol. in ether. IV, b0.02 93-4, d420 0.9346, nD20
1.5278, stable for months in the dark in evacuated sealed ampoules, gradually turns brown in the light and rapidly
resinifies in the air, readily reduces NH3-AgNO3 and Fehling soln., gives a red-violet color with fuchsin-SO2,
dissolves rapidly in NaHSO3; semicarbazone, m. 166-7; 2,4-dinitrophenylhydrazone, red, m. 132-3. VIII, b12
160-2, nD20 1.4458, d420 0.9073, stable toward Br but attacked by alk. KMnO4; amide, oil; tribromoanilide,
semi-solid; p-bromophenacyl ester, m. 56. The same acid and ester were obtained by hydrogenation of
citrylideneacetic acid prepd. according to Verley (Bull. soc. chim. 21, 414(1899)). IX, b0.03 102-5, nD20 1.5119,
d420 0.9239.
Bibliographic Information
Pyrolysis of geraniol and geranial. Doeuvre, J.; Desmule, R. Bull. soc. chim. [5] (1936), 3 196-206.
Journal language unavailable. CAN 30:22304 AN 1936:22304 CAPLUS (Copyright 2003 ACS)
Abstract
On account of the structural analogy existing between geraniol (I) and rubber, represented by a long chain of
isoprene (II) groups, a study of the pyrolysis products of I has been made. A mixt. of 100 g. of essence of
citronella, 100 g. of finely powd. dry CaCl2 and 200 cc. of anhyd. benzene was kept at 0 for 24-48 hrs. and was
then filtered. The residue was washed with 100 cc. benzene, dried, decomposed with H2O, and I was sepd. by
distn. A 3-fold repetition of this purification gave pure I, b12 112-13, []D 0, d416 0.882, d417 0.881, nC16
1.4744, nD16 1.4784, nF16 1.4867, 17 0.084 c. g. s., 17 30.4 dynes/cm., parachor 415.5; p-xenylurethan, m. 69
(C. A. 24, 334). The pyrolysis was carried out in a 60-cm. Pyrex tube at 505-10 under reduced pressure and the
products were collected in a flask at room temp. and tubes at 0 and -80. The decompn. of 100 g. of I at 9 g. per
hr. at 160 mm. gave 1 l. isobutene (III), 1 g. HCHO (polymerized), 8 g. II, 2 g. MeCH:CHCHO (IV), 4 g.
Me2C:CHCHO (V), 10 g. hydrocarbons C10H18 (VI), together with H2O, EtOH, non-condensable gases, various
liquid fractions and a residue, b13 above 118. III condensed in the tube at -80 and was volatilized and
brominated by passage through a soln. of Br in CCl4, giving Me2CBrCH2Br, b. 148-50, nD20 1.5119. II was
sepd. by 2 rectifications through a Robert column and yielded a colorless, strong-smelling liquid, b750 33.8-4.1,
d420 0.681, nD20 1.4130, which gave a yellow ppt. with HgSO4 and combined with 2 mols. of HBr to form
Me2CBrCH2CH2Br. The fraction b. 98-102 contained IV, identified by its 2,4-dinitrophenylhydrazone, m. 192.
The fraction b. 130-2 contained V, which was isolated as the semicarbazone, m. 240 (decompn.); p-
nitrophenylhydrazone, m. 161 2,4-dinitrophenylhydrazone, m. 187-8. Me2C:CHCH2OH (VII), b. 140 (Ac
deriv., b. 152) (Courtot, Bull. soc. chim. 35, 660(1906)), may have been present in the fraction b750 143-52. The
fraction VI was distd. over Na and gave a mixt.
of dimethyloctadienes, b20 67-8, d418 0.782, nC18 1.4490, nD18 1.4522, nF18 1.4601, M. R. 47.37, 47.66 and
48.38 (calcd. for c, d and f 47.16, 47.45 and 48.10). The presence of 2,6-dimethyl-2,6-octadiene (VIII) in this mixt.
was shown by the above consts., by the correspondence of the dispersion 142 to that of an alkadiene, and by a study
of the products of ozonolysis which showed no terminal CH2 group, gave AcH, showed the presence of
AcCH2CH2CHO and tested for 127% isopropylidene groups. This high proportion of Me2CO indicated the
presence of a certain amt. of 2,7-dimethyl-2,6-octadiene (IX). The single bond between the C atoms 4 and 5 of I is
doubly conjugated and is a weak linkage from the thermal standpoint. Dimidiation (bisection) by rupture of the
chain at this point, together with a H atom shift, should give III and VII. It is probable that, during the pyrolysis,
VII is dehydrated to II and that it, in part, undergoes dehydrogenation to V which, in turn, loses CO to yield III.
The free H produced in the operation may reduce I to VIII which escapes decompn. by reason of the shorter duration
of the operation. The groups Me2C:CHCH2 formed by the initial cleavage may unite to form IX. I may form an
inner oxide which in turn may cleave by pyrolysis to yield HCHO and geraniolene or by a different cleavage may
produce CH2:CH2 and methylheptenone. A similar pyrolysis of geranial (citral) (X) was carried out in the hope of
obtaining abundant yields of V by dimidiation. X disintegrated almost entirely and gave some II but very little V.
Much III was formed together with a quantity of a hydrocarbon C9H16 (probably geraniolene) and some amt. of
dimethyloctadienes identical with VI. The pyrolysis of X is very different from that of I and this is attributed to the
influence of the conjugation of the CO group. The cleavage of the mol.
no longer takes place at the 4,5-linkage since its stability seems to have been increased by the presence of the double
conjugation on the one hand and a single double bond on the other and dimidiation no longer takes place.
Bibliographic Information
Polymerization of styrene, citral and heptaldehyde. Thompson, Howard E.; Burk, Robert E. J. Am. Chem.
Soc. (1935), 57 711-13. CODEN: JACSAT ISSN: 0002-7863. Journal language unavailable. CAN
29:25625 AN 1935:25625 CAPLUS (Copyright 2003 ACS)
Abstract
Citral and heptaldehyde are stable in the substantial absence of O2; styrene continues to polymerize under these
conditions but at a diminished rate; the polymerization is probably still governed by catalysts. The effect of certain
catalysts and inhibitors is reported.
Bibliographic Information
Synthesis of dehydrogeranic acid and other compounds from -methyl--butenal. Fischer, F. G.;
Lowenberg, K. Ann. (1932), 494 263-84. Journal language unavailable. CAN 26:33697 AN
1932:33697 CAPLUS (Copyright 2003 ACS)
Abstract
-Methyl--butenal (I) (improved prepn. given; cf. F., Ertel, and L., C. A. 25, 2414) with aq. Ba(OH)2 in Et2O
gives (after repeated fractional distn.) impure dehydrocitral (II), b0.3 81-4 [semicarbazone, m. 223 (decompn.)],
and impure -methyl--heptadien--one (III) [the pure ketone, b9 83-3.5, is prepd. from I and COMe2 in EtOH-
NaOEt] [semicarbazone, m. 192 (decompn.)]; III is formed by hydrolytic fission of II or the intermediate aldol. I
is converted by NaNH2 in dry Et2O and N2 into 2-formyl-1,1,5-trimethyl-2,4-cyclohexadiene (IV) (50% yield), b9
85-6 (semicarbazone, m. 213 oxidized by O3 in EtCl at-30 to , -dimethyllevulic acid (1 mol.) and HCO2H (2
mols.), and reduced to 2,2,4-trimethylhexahydrobenzaldehyde (semicarbazone, m. 222-3), which is readily
autoxidized to 2,2,4-trimethylhexahydrobenzoic acid, m. 93. IV, COMe2 and NaNH2 in N2 give 1,1,5-trimethyl-
2--keto--butenyl-2,4-cyclohexadiene, b0.8 102-5 [semicarbazone, m. 190-1 (decompn.) ]. Citral is
converted by NaNH2 in Et2O into a compd., C20H30O (probably 2-formyl-1-methyl-1,5-di--isohexenyl-2-4-
cyclohexadiene), b9 203-5, while crotonaldehyde similarly gives resinous material. I, CH2BrCO2Et and Zn in
C6H6 give (after distn. of the intermediate with Zn dust) Et -methylsorbate, b9 82-3, hydrolyzed to -
methylsorbic acids II, b9 123-4, m. 17 (main product), and I, m. 109-10, both of which are reduced catalytically
to isoheptoic acid. Hydrolysis of the twice-distd. ester from III, CH2BrCO2Et, and Zn affords ,-dimethyl--
octa-trienoic acid (V), m. 187-8 (decompn.), identical with the dehydrogeranic acid of Cahn, Penfold and Simonsen
(C. A. 26, 1241); hydrolysis of the once distd. ester gives a little V and (mainly) an oily acid, which when heated at
50-95 loses CO2, forming the readily polymerized ,-dimethyl--heptatriene, b10 53-4, m. -23to -22.
Bibliographic Information
Conjugated double bonds. XXIV. Synthesis of cis-trans isomeric methylated polyenecarboxylic acids;
synthesis and configuration of dehydrogeranic acid. Kuhn, Richard; Hoffer, Max. Ber. (1932), 65B
651-60. Journal language unavailable. CAN 26:33696 AN 1932:33696 CAPLUS (Copyright 2003
ACS)
Abstract
Compds. with more than 2 conjugated double bonds have hitherto been obtained synthetically in only 1 of the
numerous possible cis-trans isomeric forms, although such isomers occur in nature (e. g., the eleostearic acids and
the bixins). Kuhn and Hoffer have now found that the introduction of side-chain Me groups makes possible the
prepn. of a series of polyenecarboxylic acids in geometrically isomeric forms. Attempts to synthesize natural
dehydrogeranic acid, Me2C:CHCH:CHCMe:CHCO2H (I), m. 186 (Cahn, Penfold and Simonsen, C. A. 26, 1241)
by the series of reactions Me2C:CHCHO + Me2CO (+NaOH) Me2C:CHCH:CHCOMe + BrCH2CO2Me (+Zn)
Me2C:CHCH:CHCMe(OH)CH2CO2Me (+Ba(OH)2) I gave a product (II) m. 137. As I and II are very
similar to each other and to MeCH:CHCH:CHCH:CHCO2H spectroscopically, the difference between I and II
cannot be ascribed to differences in the positions of the double bonds. There was already some evidence in the
literature that the Reformatskii synthesis may yield isomeric products, and a systematic study of the synthesis as
applied to singly and doubly unsatd. Me ketones, RCH:CHCOMe and RCH:CHCH:CHCOMe, revealed that with
Zn and BrCH2CO2Me they give, when R = Me, HO esters, Me(CH:CH)nCMe(OH)CH2CO2Me (n = 1 or 2), but
when R = Ph they form directly the unsatd. esters Ph(CH:CH)nCMe:CHCO2Me. The HO ester from
MeCH:CHCOMe gives, after elimination of water and sapon., a mixt. of 2 isomeric acids consisting chiefly (93-6%)
of -methylsorb c acid (III), m. 120 (Burton and Ingold, C. A. 24, 59), but if the HO ester is treated directly with
boiling concd. Ba(OH)2 there is obtained in poor yield an oily acid which is rapidly and completely converted by
hot NaOH into an isomer (IV) of III, m. 98-9 (1 g. from 16 g. HO ester). B. and I.'s acid m. 74-6 was probably
this compd. in impure form; a mixt. of about equal parts III and IV m. 74-6 and cannot be sepd. by fractional
crystn. from dil. alc. From their method of prepn. and their phys. consts.
it is very probable that III and IV differ in their geometrical configuration at the double bond adjacent to the CO2H
group. Me(CH:CH)2COMe likewise gave a HO ester (V), dehydrated by KHSO4 or P2O5 to a Me -
methyloctatrienate (VI) which on sapon. gave a mixt. of 2 isomeric acids, also obtained directly from V with
Ba(OH)2. The Me -styrylcrotonate (VII), obtained directly from PhCH:CHCOMe, yields on sapon. almost
exclusively (94%) an acid (3-methyl-5-phenyl-2,4-pentadienic 1-acid), m. 124, which is converted into an isomer
m. 160 by rearrangement with I in sunlight. The Me -styrylacrylcrotonate (VIII) obtained from
Ph(CH:CH)2COMe likewise yields a mixt. of acids, m. 167-9 and 202-3, resp. With the information thus gained,
K. and H. were now able to synthesize the natural (high-melting) I by avoiding the direct sapon. of the intermediate
HO ester with Ba(OH)2. The lower-melting isomers are the more easily sol. forms. The absorption spectra of the
isomers are almost identical as regards the positions of the bands but the bands of the lower-melting isomers have a
lesser height. It is very probable, although not definitely proved, that the lower-melting isomers are the cis-forms.
Natural I would then have a configuration corresponding to citral a and geraniol, and the synthetic II would
correspond to citral b and nerol. Me 3-hydroxy-3-methyl-4-hexenate, from MeCH:CHCOMe (55% yield), b12 82-
5, b774 193-5, gives with KHSO4 or P2O6 in benzene 50-7% of Me -methylsorbate, b12 80-4. d419 0.967,
nD18 1.5010. Me 3-hydroxy-3-methyl-4,6-octadienate (V) (30% yield), b2 90-105, easily autoxidizes in the air to
a yellow viscous sirup. VI (50% yield), yellowish, b11 117-25, also readily autoxidizes and polymerizes; at 0 it
partially seps. in crystals m. 33. The free 3-methyl-2,4,6-octatrienic 1-acids m. 160-1 (cor.) (yield, 5 g. crude or 3
g. pure acid from 8 g. ester), and 105-10 (yield, 1.0-1.2 g.). 6-Methyl-3,5-heptadien-2-one (43% from
Me2C:CHCHO and Me2CO), b115 86-7 d419 0.
897, nD19 1.5292, soon changes to a viscous yellow sirup in the air; oxime, m. 108-9 (cor., Berl). Me ester of I,
very un-stable, b12 127-35. VII (30 g. from 72 g. PhCH:CHCOMe), b12 170-2, d417 1.065, nD17 1.6258. VIII
(Me 3-methyl-7-phenyl-2,4,6-heptatrien-1-ate) (12% yield), viscous yellow oil, b0-3 160-80.
Bibliographic Information
Formation of bases from carbonyl compounds. Skita, A.; Keil, F. Techn. Hochschule, Hanover, Ber.
(1928), 61B 1452-9. Journal language unavailable. CAN 22:37663 AN 1928:37663 CAPLUS
(Copyright 2003 ACS)
Abstract
Reduction of Schiff bases to secondary amines gives different yields, depending on the nature of the base. Thus,
while PhCH:NPh is reduced almost quant. to PhCH2NHPh by the ordinary reducing agents, the yields decrease very
rapidly with increasing mol. wt. of the radicals attached to the N and with Schiff bases contg. unsatd. residues, as
these unstable substances often easily escape reduction as the result of polymerization or hydrolysis. For this
reason recourse had already been had in some cases (e. g., in the prepn. of Ph(CH2)3NHEt from PhCH:CHCH:NEt;
cf. C. A. 21, 2882) to catalytic reduction with colloidal Pt in acid soln. But this method also gives no appreciable
quantities of basic reduction products with more unstable imino compds. (e. g., citralmethylamine (I)); evidently the
hydrolytic action of the acids is more rapid than the hydrogenation velocity. Whereas a Schiff base in neutral soln.
or suspension takes up either no H or only an insufficient quantity, addn. of NH3 to the colloidal Pt results in a
vigorous absorption of H and the formation of the corresponding secondary base. Amines exert a similar catalytic
influence. In fact, in many cases it is better not to start with the preformed Schiff bases but with a mixt. of their
components (aldehyde and amine). Thus, citral and a slight excess of MeNH2 yielded considerably more N-
methyl-3,7-dimethyloctylamine (II) than did I. Under the proper conditions citral in NH4OH suspension gives no
primary amine but only the secondary bis[3,7-dimethyloctyl]amine (III). While other aldehydes of high mol. wt.
yield secondary amines in the same way (e. g., diheptylamine (IV) from enanthaldehyde), the initial members of the
aldehyde series (AcH, EtCHO) yield the tertiary amines. Ketones with NH3 or primary amines in aq. suspension
also yield secondary bases. Citralcyclohexylamine, b18 170-2, gives in alc. with colloidal Pt and AcOH N-
cyclohexyl-3,7-dimethyloctylamine, b14 151-3; HCl salt, m. 154-5; picrolonate, m. 174-5.
Citralisoamylamine, b20 150-4, in neutral alc. soln. yields N-isoamyl-3,7-dimethyloctylamine, b17 142-5; HCl
salt, m. 168-9; picrolonate, m. 186-7. Citralethylamine, very unstable, b12 113-5, in neutral soln. yields at most
2% of N-ethyl-3,7-dimethyloctylamine (V) but 9 g. of the base in 50 cc. alc. with 3 cc. of 25% NH3 and 100 cc. of
1% Pt (contg. 1 g. gelatin) absorbs the calcd. quantity of H in 1.5 hrs. at room temp. under 3 atm. excess pressure
and yields 5 g. V, b13 135-7; HCl salt, m. 102-3; NO deriv., oil; picrolonate, m. 196-7. I, b13 107-9 (in H).
III, from 16.2 g. citral and colloidal Pt (prepd. from 30 cc. H2PtCl6, 20 cc. 1% colloidal Pt and 20 cc. 10% gum
arabic) suspended in 40 cc. H2O, treated with 7.5 cc. 24% aq. NH3 and hydrogenated at room temp. under 3 atm.
excess pressure, b15 191-3; HCl salt, m. 141-2. IV, m. 30, b. 270-2; HCl salt, m. 250, is not hygroscopic.
(iso-Pr)2NH, from Me2CO in aq. NH4OH, b. 84; HCl salt (5 g. from 15 g. Me2CO), m. 212-4; picrate, m. 140.
MeCOEt gives (MeEtCH)2NH, b. 230-3, whose HCl salt is not deliquescent but, when pure, is stable in the air and
m. 215-6. Et2CO gives (Et2CH)2NH. From cyclohexanone is obtained dicyclohexylamine, b20 128-30 HCl
salt, m. around 340. MeCOEt and aq. EtNH2 give EtNHCHMeEt, b. 96-8. N-Ethylcyclohexylamine, from
cyclohexanone and EtNH2, b. 161.
Bibliographic Information
A fragrant product. Dupont. (1905), FR 355326 19050617 Patent language unavailable. CAN
1:6838 AN 1907:6838 CAPLUS (Copyright 2003 ACS)
Patent Family Information
Patent No. Kind Date Application No. Date
FR 355326 19050617 FR
Abstract
Process of manufacturing a fragrant product, consisting in condensing citrol and chloracetone in the absence of
water with condenstation agents. To a mixture, cooled to 3, composed of citral, 1.200 kg., chloracetone, 1,200, dry
benzene, 4,800, there is added sodamide, 20%, the product stirred for 8 hours at a low temperature, and left over
night at the ordinary temperature, when the mass is extracted by a solvent which is afterwards eliminated, followed
by distillation in vacuo, gathering the fraction between 170-200, redistilling and collecting the distillate going over
at 175, and polymerizing, at a low temperature and under 12 mm. pressure. A better method is to employ
phosphoric acid of 63, B.acte.e., and operate under 40.
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